Barrier-enhanced polymer film structures, methods for preparing same, and articles thereof

Abstract

To provide a film for packaging applications having improved barrier properties, toughness, and snap properties. [Solution] Provided are rigid or flexible polyethylene or ethylene / α-olefin copolymer-based coextruded multilayer films or sheets for thermoforming into formed containers, such as packaging containers. In particular, rigid films have improved barrier properties, toughness, and snap properties. The films comprise one or more stacks of polypropylene layers. In one embodiment, the polypropylene layers have different microstructures, with any two adjacent layers having different microstructures and / or crystallinity levels, providing an interface or interphase between the two layers. The overall polypropylene stack structure helps impede oxygen transport, providing a laminate or structure (such as a rigid film or sheet) with enhanced oxygen barrier properties.

Description

[Technical Field]

[0001] (CROSS-REFERENCE TO RELATED APPLICATIONS) This application claims the benefit of U.S. Provisional Patent Application No. 63 / 065,662, filed August 14, 2020, U.S. Provisional Patent Application No. 63 / 173,784, filed April 12, 2021, and U.S. Provisional Patent Application No. 63 / 184,650, filed May 5, 2021, the entireties of which are incorporated herein for all purposes.

[0002] The present invention relates to packaging applications. The invention generally relates to a rigid or flexible polyethylene- or ethylene / α-olefin copolymer-based coextruded multilayer film or sheet for thermoforming into a shaped container, such as a packaging container. Among other things, the film has improved barrier properties, toughness, and snap properties. In particular, the film of the present invention comprises one or more stacks of polypropylene layers. In one embodiment, the polypropylene layers in the stack are provided so that any two adjacent layers have different microstructures, possibly providing an interface or interphase between the two layers with different microstructures and / or crystallinity. The overall polypropylene stack structure helps impede oxygen transport, thereby providing a laminate or structure, e.g., a rigid film or sheet, with enhanced oxygen barrier properties. The invention also relates to a process for preparing shaped articles, such as containers, from such films, as well as to such shaped articles, both rigid or flexible, filled and unfilled. [Background technology]

[0003] Packaging is a key component for the storage and transportation of many consumer or industrial items. Food and beverages, household chemicals, cosmetics, consumer goods, medical products, and industrial products are examples of areas where packaging plays a key role in the storage and transportation of products. Historically, ceramics, metals, and glass were utilized for storage and transportation. However, the mobility associated with modern life has created a demand for more flexibility in container design and reduced costs associated with packaging and transportation. The development of polymeric materials and related processing techniques has met this demand by introducing opportunities to replace historical materials with polymer solutions. However, many current solutions have limited recycling value, which negatively impacts sustainability. The present invention addresses the issue of recyclability and sustainability.

[0004] In the rigid polymer container space, containers are made using equipment such as form-fill-seal (FFS), in which a roll of film is unwound and thermoformed into a container. Such rigid containers are used in the following industries, among others: (1) food, (2) medical, (3) cosmetics, (4) automotive, and (5) electronics. Rigid plastic sheets for preparing such containers are made from polystyrene (PS), high impact polystyrene (HIPS), polyethylene terephthalate (PET), polylactic acid (PLA), polypropylene (PP), etc.

[0005] Polypropylene is the second most common commodity thermoplastic in the world after polyethylene. Polyethylene is generally preferred for packaging applications in a variety of food, medical, commercial, and automotive applications. While polypropylene exhibits high heat resistance, optical clarity, flexibility, low-temperature impact properties, and overall structural rigidity, it is not the preferred material for such applications. Polystyrene is preferred, particularly for barrier applications, i.e., when a barrier to oxygen and moisture transport is required.

[0006] Barrier properties in terms of inhibiting oxygen and moisture transfer are desirable in such rigid plastic sheets to avoid damage to the goods and to extend shelf life, especially in the food and beverage sector, which is limited by definition. Currently available barrier materials include high-cost, high-density barrier films such as ethylene-vinyl alcohol (EVOH) or polyamide (PA, PA6, PA66), which are used as laminates or in multilayer coextrusion processes with traditional substrate materials such as polystyrene and polypropylene.

[0007] In general, polymeric materials that function as barriers to water vapor and certain gases, such as oxygen and / or carbon dioxide, can be utilized to form molded polymeric articles that function as packaging materials. For example, such effectiveness in terms of barrier properties can enable the polymeric material and the resulting molded polymeric article to extend the shelf life of products stored therein.

[0008] The barrier properties against water vapor and gases can vary depending on the particular polymeric material utilized. For example, some polymeric materials have been found to function effectively as good barrier materials against water vapor and poor barrier materials against gases, while other polymeric materials function as poor barrier materials against water vapor and good barrier materials against gases. In some cases, techniques or treatments can be used to provide polymeric materials that can function as effective barriers against both water vapor and these gases. However, these treatments can affect the aesthetic properties (e.g., transparency) of the packaging material and can also adversely affect the mechanical properties of such materials, especially when the material has a relatively large thickness.

[0009] Aside from barrier, mechanical, and optical properties, certain polymeric materials may also be ineffective for forming shaped polymeric articles according to certain forming or molding processes. Finally, recycling of some current polymeric materials can be complicated by the particular techniques or processes used to create the barrier properties, resulting in undesirable and inefficient waste streams.

[0010] Another desirable property is the processability of the polymer to make a rigid film. For example, polystyrene is an amorphous thermoplastic polymer with high mechanical strength, lower shrinkage, and a wide processing window. Polystyrene is considered the standard material for commodity products and packaging applications due to its ease of processing, whether by injection molding or extrusion / thermoforming / form-fill-seal processes.

[0011] In comparison, polypropylene is a semi-crystalline thermoplastic polymer with good mechanical properties, high heat and chemical resistance, but a much higher shrinkage rate with a narrow processing window. Therefore, polystyrene has a clear advantage over polypropylene in applications using extrusion, thermoforming, and form-fill-seal processing techniques. Furthermore, polypropylene requires auxiliary heating and cooling, apart from its higher shrinkage rate.

[0012] The rigid film of the present invention, which comprises a stack of polypropylene layers, provides an alternative to the above-mentioned polymer sheets for container packaging with improved properties, at a lower cost, and without sacrificing the performance standards of the packaging container in the above-mentioned fields. Despite comprising polypropylene, the rigid film of the present invention has a lower shrinkage rate and is processable similarly to polystyrene.

[0013] In fact, the rigid films of the present invention offer high performance in terms of oxygen and water vapor transmission rates comparable to those of conventional polypropylene and polystyrene. Therefore, the rigid films of the present invention are a low-cost barrier option for shelf life extension, for example, in rigid container applications. These rigid films also exhibit comparable toughness and snap properties. In summary, these films (i) exhibit amenability to processing on existing equipment designed for conventional polypropylene or polystyrene, but with reduced shrinkage, and (ii) exhibit compatibility with existing lamination, printing, thermoforming, and form-fill-seal processes. Finally, despite such desirable properties and processability, the rigid films of the present invention provide a lighter material with increased recyclability compared to conventional high-density thermoplastics, thus improving downstream sustainability.

[0014] As a result, there is a need to provide molded polymeric articles with improved aesthetic properties that function as an effective barrier to water vapor and certain gases, while also exhibiting desirable physical properties that are sustainable over multiple uses or lifecycles. Although the description of the exemplary embodiments focuses on rigid sheets, the present invention applies equally to flexible and semi-rigid sheets. Summary of the Invention

[0015] In one embodiment, the present invention provides a coextruded multilayer polymer film comprising at least one bilayer stack A-B1 or A-B2, wherein a first layer of the bilayer stack is A and a second layer of the bilayer stack is either B1 or B2; A is a layer mainly containing polypropylene, B1 is a layer mainly containing polypropylene and 50% by weight or less of a hydrocarbon resin; B2 is a layer containing primarily IMPEDE® polymer; The two layers in the two-layer stack are contiguous adjacent to one another in a coextruded multilayer polymer film.

[0016] In another embodiment, the present invention relates to a coextruded multilayer polymer film as described above, further comprising one layer from the following set of layers, or two or more layers from the following set of layers: (A) at least one layer primarily comprising a polyolefin; (B) at least one layer comprising primarily polypropylene; (C) at least one layer comprising primarily IMPEDE®; (D) at least one layer comprising primarily polypropylene and up to 50% by weight of a hydrocarbon resin; (E) at least one layer comprising predominantly a polyethylene polymer or interpolymer; (F) at least one barrier layer comprising EVOH; (G) at least one barrier layer comprising primarily nylon; (H) at least one barrier layer comprising primarily polyester; (I) at least one tie layer, and (J) Combination of the above layers.

[0017] In yet another embodiment, the present invention provides a coextruded multilayer polymeric film as described above, comprising: (I) an outer layer comprising polyethylene; (II) a core layer comprising EVOH; (III) an inner layer comprising polyethylene; At least one of the three layers relates to a coextruded multilayer polymer film comprising a two-layer stack.

[0018] In one embodiment, the present invention relates to a coextruded multilayer polymeric film as described above, wherein the outer layer and the inner layer comprise a two-layer stack.

[0019] In another embodiment, the present invention relates to a coextruded multilayer polymeric film as described above, comprising three layers in the following order: (I) a first layer comprising primarily polypropylene; (II) (a) Predominantly polypropylene and not more than 50% by weight of hydrocarbon resins; or (b) a second layer comprising primarily IMPEDE® polymer; and (III) A third layer comprising primarily polypropylene.

[0020] In yet another embodiment, the present invention provides a method for producing a (I) an outer layer stack comprising one or more layers, (A) optionally, at least one layer of the outer layer stack comprises a polyethylene polymer or a polyethylene interpolymer; (B) Optionally, the outer layer stack comprises: (i) a layer comprising primarily polypropylene; (ii) (a) Predominantly polypropylene and not more than 50% by weight of hydrocarbon resins; or (b) a layer comprising primarily IMPEDE® polymer; an outer layer stack, in which two layers in the two-layer stack are contiguous with one another; (II) a core layer stack comprising one or more layers, (C) optionally, at least one layer of the core layer stack comprises a polyethylene polymer or a polyethylene interpolymer; (D) Optionally, the core layer stack comprises: (iii) a layer comprising primarily polypropylene; (iv) (a) Predominantly polypropylene and not more than 50% by weight of hydrocarbon resins; or (b) a layer comprising primarily IMPEDE® polymer; the two layers in the two-layer stack are contiguous and adjacent to each other; (E) optionally, a core layer stack, wherein at least one layer of the core layer stack comprises EVOH; and (III) an inner layer stack comprising one or more layers, (F) optionally, at least one layer of the inner layer stack comprises a polyethylene polymer or a polyethylene interpolymer; (G) Optionally, the inner layer stack comprises: (v) a layer comprising primarily polypropylene; (vi) (a) Predominantly polypropylene and not more than 50% by weight of hydrocarbon resins; or (b) a layer comprising primarily IMPEDE® polymer; two layers in the two-layer stack include an inner layer stack that is contactably adjacent to one another; The polyethylene interpolymer is (a) optionally, 0.894 to 0.908 g / cm 3 a first ethylene / α-olefin copolymer fraction having a density in the range of 0.2 to 1 dg / min; (b) optionally, between about 0.910 and 0.924 g / cm 3 a second ethylene / α-olefin copolymer fraction having a density in the range of 0.5 to 2 g / 10 min, a melt index in the range of 0.5 to 2 g / 10 min, a zero shear viscosity ratio (ZSVR) in the range of about 1.15 to 2.5, and a molecular weight distribution, expressed as the ratio of weight average molecular weight to number average molecular weight (Mw / Mn), in the range of 2.0 to 4.0.

[0021] In one embodiment, the present invention relates to a coextruded multilayer polymer film as described above, comprising a number of layers selected from the range of 2-100.

[0022] In another embodiment, the present invention relates to the coextruded multilayer polymer film described above, wherein the weight percentage of the EVOH copolymer relative to the coextruded multilayer polymer film ranges from about 0.1% to about 10%.

[0023] In yet another embodiment, the present invention relates to the coextruded multilayer polymer film described above, wherein the mole percent of ethylene in said EVOH copolymer ranges from about 10% to about 55%.

[0024] In one embodiment, the present invention relates to the coextruded multilayer polymer film described above, wherein the coextruded multilayer polymer film exhibits a DTUL of 30° C. or greater and a secant modulus of 500 MPa or greater.

[0025] In another embodiment, the present invention relates to a coextruded multilayer polymer film as described above, wherein the film thickness ranges from about 5 μm to about 1600 μm.

[0026] In yet another embodiment, the present invention relates to the coextruded multilayer polymer film described above, wherein the hydrocarbon resin in the second layer B1 comprises an aliphatic hydrocarbon resin, an aliphatic / aromatic hydrocarbon resin, an aromatic hydrocarbon resin, a polyterpene resin, a terpene phenolic resin, a rosin ester, a rosin acid, or a mixture thereof.

[0027] In one embodiment, the present invention relates to the coextruded multilayer polymer film described above, wherein the hydrocarbon resin in the second layer B1 is partially hydrogenated or fully hydrogenated.

[0028] In another embodiment, the present invention relates to the coextruded multilayer polymer film described above, wherein the hydrocarbon resin in the second layer B1 comprises polycyclopentadiene.

[0029] In yet another embodiment, the present invention relates to the coextruded multilayer polymer film described above, wherein the hydrocarbon resin in the second layer B1 has a weight average molecular weight of from about 400 g / mol to about 5,000 g / mol.

[0030] In one embodiment, the present invention relates to the coextruded multilayer polymer film described above, wherein the hydrocarbon resin comprises an aromatic C9 hydrogenated resin having a Ring and Ball softening point of about 110°C or greater.

[0031] In another embodiment, the present invention provides a 3.0 cm 3 / m 2 / day or less water vapor transmission rate, and / or 60 cm 3 / 100in 2The coextruded multilayer polymer film is characterized by an oxygen transmission rate of 1000 kJ / day or less.

[0032] In yet another embodiment, the present invention relates to the coextruded multilayer polymer film described above, wherein the second layer B1 further comprises a nucleating agent selected from sodium benzoate, talc, glycerol alkoxide salts, cyclic carboxylates, bicyclic carboxylates, glycerolates, phosphines, phosphates, diols, hexahydrophthalates, amides, and sugar alcohols.

[0033] In one embodiment, the present invention provides a method for preparing a nucleating agent comprising: Mannitol or a mannitol-based compound, sorbitol or a sorbitol-based compound, nonitol or a nonitol-based compound, 1,2,3-trideoxy-4,6:5,7-bis-0-((4-propylphenyl)methylene)nonitol, 2,4,8,10-tetra(tert-butyl)-6-hydroxy-12H-dibenzo[d,g][1,3,2]dioxaphosphocin 6-oxide, a salt of 2,4,8,10-tetra(tert-butyl)-6-hydroxy-12H-dibenzo[d,g][1,3,2]dioxaphosphocin 6-oxide, a sodium salt of 2,4,8,10-tetra(tert-butyl)-6-hydroxy-12H-dibenzo[d,g][1,3,2]dioxaphosphocin 6-oxide, hydroxy-bis[2,2'-methylenebis[4,6-di(tert-butyl)phenyl]phosphate, 2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphate, salts thereof, sodium salts thereof, aluminum salts thereof, and lithium salts thereof; (1R)-1-[(4R,4aR,8aS)-2,6-bis(3,4-dimethylphenyl)-4,4a,8,8a-tetrahydro-[1,-3]dioxino[5,4-d][1,3]dioxin-4-yl]ethane-1,2-diol, 1-[8-propyl-2,6-bis(4-propylphenyl)-4,4a,8,8a-tetrahydro-[1,3]dioxino[5,4-d][1,3]dioxin-4-yl]ethane-1,2-diol, N-[3,5-bis(2,2-dimethylpropanoylamino)phenyl]-2,2-dimethylpropanamide), (1S,2R)-cyclohexane-1,2-dicarboxylate salt and zinc octadecenoate, (1S,2R)-cyclohexane-1,2-dicarboxylate calcium salt and zinc octadecenoate, cis-endo-bicyclo[2,2,1]heptane-2,3-dicarboxylic acid disodium salt and 13-docosenamid, amorphous silicon dioxide, Bicycloheptanedicarboxylic acid, bicyclo[2.2.1]heptanedicarboxylate, Cyclohexanedicarboxylic acid, the calcium salt of cyclohexanedicarboxylic acid, a blend of cyclohexanedicarboxylic acid, the calcium salt of cyclohexanedicarboxylic acid, and zinc stearate, and The present invention relates to the coextruded multilayer polymer film described above, wherein the nucleating agent is selected from a mixture of two or more of these.

[0034] In another embodiment, the present invention relates to a molded polymeric article comprising the coextruded multilayer polymeric film described above.

[0035] In yet another embodiment, the present invention relates to the shaped polymeric article described above, wherein the shaped polymeric article is a thermoformed shaped polymeric article.

[0036] In one embodiment, the present invention relates to a shaped polymeric article as described above that is a container for packaging food products.

[0037] In another embodiment, the present invention relates to the container described above, wherein the coextruded multilayer polymeric film further comprises one layer from the following set of layers, or two or more layers from the following set of layers: (A) at least one layer primarily comprising a polyolefin; (B) at least one layer comprising primarily polypropylene; (C) at least one layer comprising primarily IMPEDE®; (D) at least one layer comprising primarily polypropylene and up to 50% by weight of a hydrocarbon resin; (E) at least one layer comprising predominantly a polyethylene polymer or interpolymer; (F) at least one barrier layer comprising EVOH; (G) at least one barrier layer comprising primarily nylon; (H) at least one barrier layer comprising primarily polyester; (I) at least one tie layer, and (J) Combination of the above layers.

[0038] In yet another embodiment, the present invention relates to a coextruded multilayer polymer film comprising: (I) an outer layer comprising polyethylene; (II) a core layer comprising EVOH; (III) an inner layer comprising polyethylene; The container described above, wherein at least one of the three layers comprises the two-layer stack.

[0039] In one embodiment, the present invention relates to the container described above, wherein the outer layer and the inner layer comprise a two-layer stack.

[0040] In another embodiment, the present invention relates to the container described above, wherein the coextruded multilayer polymeric film comprises three layers in the following order: (I) a first layer comprising primarily polypropylene; (II) (a) Predominantly polypropylene and not more than 50% by weight of hydrocarbon resins; or (b) a second layer comprising primarily IMPEDE® polymer; and (III) A third layer comprising primarily polypropylene.

[0041] In yet another embodiment, the present invention provides a coextruded multilayer polymeric film comprising: (I) an outer layer stack comprising one or more layers, (A) optionally, at least one layer of the outer layer stack comprises a polyethylene polymer or a polyethylene interpolymer; (B) Optionally, the outer layer stack comprises: (i) a layer comprising primarily polypropylene; (ii) (a) Predominantly polypropylene and not more than 50% by weight of hydrocarbon resins; or (b) a layer comprising primarily IMPEDE® polymer; an outer layer stack, in which two layers in the two-layer stack are contiguous with one another; (II) a core layer stack comprising one or more layers, (C) optionally, at least one layer of the core layer stack comprises a polyethylene polymer or a polyethylene interpolymer; (D) Optionally, the core layer stack comprises: (iii) a layer comprising primarily polypropylene; (iv) (a) Predominantly polypropylene and not more than 50% by weight of hydrocarbon resins; or (b) a layer comprising primarily IMPEDE® polymer; the two layers in the two-layer stack are contiguous and adjacent to each other; and (E) optionally, a core layer stack, wherein at least one layer of the core layer stack comprises EVOH; and (III) an inner layer stack comprising one or more layers, (F) optionally, at least one layer of the inner layer stack comprises a polyethylene polymer or a polyethylene interpolymer; (G) Optionally, the inner layer stack comprises: (v) a layer comprising primarily polypropylene; (vi) (a) Predominantly polypropylene and not more than 50% by weight of hydrocarbon resins; or (b) a layer comprising primarily IMPEDE® polymer; two layers in the two-layer stack include an inner layer stack that is contactably adjacent to one another; The polyethylene interpolymer is (a) optionally, 0.894 to 0.908 g / cm 3 a first ethylene / α-olefin copolymer fraction having a density in the range of 0.2 to 1 dg / min; (b) optionally, between about 0.910 and 0.924 g / cm 3 a second ethylene / α-olefin copolymer fraction having a density in the range of 0.5 to 2 g / 10 min, a melt index in the range of 0.5 to 2 g / 10 min, a zero shear viscosity ratio (ZSVR) in the range of about 1.15 to 2.5, and a molecular weight distribution, expressed as the ratio of weight average molecular weight to number average molecular weight (Mw / Mn), in the range of 2.0 to 4.0.

[0042] In one embodiment, the present invention relates to the container described above, wherein the coextruded multilayer polymer film comprises a number of layers selected from the range of 2 to 100.

[0043] In another embodiment, the present invention relates to the container described above, wherein the weight percentage of the EVOH copolymer relative to the coextruded multilayer polymer film ranges from about 0.1% to about 10%.

[0044] In yet another embodiment, the present invention relates to the container described above, wherein the mole percent of ethylene in said EVOH copolymer ranges from about 10% to about 55%.

[0045] In one embodiment, the present invention provides a process for preparing the coextruded multilayer polymer film described above, comprising: (I) providing a layer A1; (II) providing a layer comprising B1 or B2, A1 and B1, or A1 and B2, relate to a process in which an interface or interphase is formed at their adjacent boundary, such that the interphase provides a discontinuity in properties between the two layers, resulting in improved barrier properties of the coextruded multilayer polymer film.

[0046] In another embodiment, the present invention relates to a container for packaging food products prepared from the rigid coextruded multilayer polymeric film prepared by the process described above.

[0047] In yet another embodiment, the present invention relates to the shaped article described above, wherein the shaped polymeric article is a thermoformed shaped polymeric article.

[0048] In one embodiment, the present invention provides a laminate structure comprising a coextruded multilayer polymeric film, the polymer film comprises at least one bilayer stack A-B1 or A-B2, the first layer of the two-layer stack is A and the second layer of the two-layer stack is either B1 or B2; A is a layer mainly containing polypropylene, B1 is a layer mainly containing polypropylene and 50% by weight or less of a hydrocarbon resin; B2 is a layer containing primarily IMPEDE® polymer; the two layers in the two-layer stack are contiguous and adjacent to each other; The thickness of the laminated structure is in the range of 5 μm to 1600 μm. [Brief explanation of the drawings]

[0049] [Figure 1] 1 illustrates a multilayer embodiment of the rigid film of the present invention. [Figure 2] 1 shows the differential scanning calorimetry profile of a polypropylene pellet sample. [Figure 3] 1 shows the differential scanning calorimetry profile of a polypropylene sheet sample. [Figure 4]1 shows a cup made from the roll stock or rigid sheet of the present invention. [Figure 5] 1 also shows a cup made from the roll stock or rigid sheet of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0050] Reference will now be made in detail to the embodiments, one or more examples of which are illustrated in the drawings. Each example is provided by way of explanation of an embodiment, not as a limitation of the disclosure. Indeed, it will be apparent to those skilled in the art that various modifications and variations can be made to the embodiments without departing from the scope or spirit of the disclosure. For example, features illustrated or described as part of one embodiment can be used with another embodiment to yield a still further embodiment. Accordingly, it is intended that aspects of the present disclosure cover such modifications and variations.

[0051] I. Definitions and Terminology All percentages expressed in this patent application are by weight of the total weight of the composition unless otherwise specified.

[0052] All ratios expressed in this patent application are on a weight:weight basis unless otherwise specified.

[0053] Ranges are used solely as a shorthand to avoid listing and describing each and every value within the range. Any appropriate value within the range can be selected as the upper, lower, or endpoint of the range.

[0054] Unless the context clearly indicates otherwise, the singular form of a word includes its plural, and vice versa. Thus, references to "a," "an," and "the" generally include the plural of the respective term they qualify. For example, a reference to "a method" includes its plural, "methods." Similarly, the terms "comprise," "comprises," and "comprising," whether or not used as transitional phrases in the claims, should be interpreted inclusively rather than exclusively. Similarly, the terms "include," "including," and "or" should be interpreted inclusively unless such an interpretation is clearly prohibited by the context. Similarly, the term "example," particularly when followed by a list of terms, is merely exemplary and descriptive and should not be considered exclusive or inclusive.

[0055] The terms "comprising," "including," "having," and their derivatives are not intended to exclude the presence of any additional component, step, or procedure, whether or not it is specifically disclosed. For the avoidance of doubt, all compositions claimed through the use of the term "comprising" may include any additional additive, adjuvant, or compound, whether polymeric or not, unless stated to the contrary. In contrast, the term "consisting essentially of" excludes from the scope of any succeeding recitation any other component, step, or procedure, except those that are not essential to operability. The term "consisting of" excludes any component, step, or procedure not specifically delineated or listed.

[0056] Those skilled in the art will understand that the methods, compositions, and other advances disclosed in this patent application are not limited to the specific methodology, protocols, and reagents described herein, as these may vary. Furthermore, the terminology used in this application describes particular embodiments only and is not to be construed as limiting the scope of what is disclosed or claimed.

[0057] Unless otherwise defined, all technical and scientific terms, terminology, and acronyms used in this application have the meaning commonly understood by one of ordinary skill in the art of the invention or the field in which the term is used. Although any compositions, methods, articles of manufacture, or other means or materials similar or equivalent to those described in this patent application can be used in the practice of the present invention, the specific compositions, methods, articles of manufacture, or other means or materials are described for illustrative purposes only.

[0058] All patents, patent applications, publications, technical and / or journal articles, and other references cited or referred to in this patent application are incorporated by reference in their entirety to the extent permitted by law. The discussion of these references is intended merely to summarize the assertions made in those references. No admission is made that any such patents, patent applications, publications, or references, or any portion thereof, are relevant, important, or prior art. The right to challenge the accuracy and pertinence of any assertion of such patents, patent applications, publications, and other references as relevant, important, or prior art is expressly reserved.

[0059] As used herein, the term "composition" includes a mixture of materials that comprise the composition, as well as reaction products and decomposition products formed from the materials of the composition.

[0060] As used herein, the term "polymer" refers to a polymeric compound prepared by polymerizing monomers, whether of the same or different types. Thus, the generic term polymer encompasses the terms homopolymer (used to refer to a polymer prepared from only one type of monomer, with the understanding that trace amounts of impurities may be incorporated into the polymer structure), copolymer, and interpolymer, as defined below.

[0061] As used herein, the term "interpolymer" refers to a polymer prepared by the polymerization of at least two types of monomers. Thus, the generic term interpolymer includes copolymers (used to refer to polymers prepared from two types of monomers) and polymers prepared from more than two types of monomers.

[0062] As used herein, the term "ethylene-based polymer" refers to a polymer that, in polymerized form, comprises a majority amount of ethylene monomer (based on the weight of the polymer), and may optionally include one or more comonomers.

[0063] As used herein, the term "ethylene / α-olefin interpolymer" refers to an interpolymer that comprises, in polymerized form, a majority amount of ethylene monomer (based on the weight of the interpolymer) and one or more additional α-olefin monomers. The term "ethylene / α-olefin interpolymer" includes ethylene / α-olefin copolymers, as well as terpolymers and other polymers derived from multiple monomers.

[0064] As used herein, the term "ethylene / α-olefin copolymer" refers to a copolymer that contains, in polymerized form, a majority amount of ethylene monomer (based on the weight of the copolymer) and an α-olefin as the only two monomer types.

[0065] As used herein, the term "EVOH" refers to a polymer containing repeating units of ethylene and vinyl alcohol. As is generally known in the art, the weight ratio of ethylene to vinyl alcohol determines the barrier properties. Such polymers and their methods of manufacture are generally known in the art.

[0066] As used herein, "density" is determined by ASTM D 792 and "melt index" is determined by ASTM D 1238. The "melting point" of a polymer is measured as the peak melting point when performing differential scanning calorimetry (DSC) as described in ASTM Procedure D3417-83 (rev. 88).

[0067] II. Polymer Film Structures Generally, the present invention relates to a polymeric film structure comprising at least one stack of coextruded polypropylene ("PP") layers. The polymeric film structure may comprise one or more other layers as described herein and in the art.

[0068] In one embodiment, the present invention generally relates to a rigid film or sheet comprising at least one stack of polypropylene ("PP") layers. Such rigid films are characterized by, among other things, enhanced barrier properties, stiffness, toughness, and / or snap properties. In another embodiment, the present invention generally relates to a flexible film or sheet comprising at least one stack of polypropylene ("PP") layers. Such flexible films are characterized by, among other things, enhanced barrier properties, stiffness, and toughness.

[0069] In another embodiment, the present invention generally relates to a rigid film or sheet comprising at least one stack of polypropylene ("PP") layers, which may be coextruded or laminated. In another embodiment, the present invention generally relates to a flexible film or sheet comprising at least one stack of polypropylene ("PP") layers, which may be coextruded or laminated.

[0070] The polypropylene stack, whether rigid or flexible, can be coextruded with or laminated to other film structures, and it should be noted that in laminate structures including such polypropylene stacks, the polypropylene stack can be coextruded or laminated.

[0071] Lamination can be, for example, thermal lamination, extrusion lamination, adhesive lamination (solvent and solventless), or printing or forming or molding.

[0072] A "layer primarily comprising a certain component" means that the layer primarily comprises that component. For clarity, "primarily" means that the layer comprises more than about 40% by weight of the component. For example, if a layer primarily comprises polypropylene, that means that the weight percentage of PP in the layer is greater than about 40%.

[0073] A stack of polypropylene layers ("polypropylene stack" or "PP stack"), as described herein, means at least two layers each comprising predominantly polypropylene, and at least one other layer comprising predominantly regular polypropylene.

[0074] In one embodiment, such a stack of polypropylene layers includes at least two layers, each comprising predominantly polypropylene, wherein at least one layer comprises predominantly Impede® polypropylene as described herein and at least one other layer comprises predominantly regular polypropylene.

[0075] More specifically, in one embodiment, the present invention relates to a coextruded multilayer polymer film comprising at least one bilayer stack A-B1 or A-B2, wherein a first layer of the bilayer stack is A and a second layer of the bilayer stack is either B1 or B2, wherein A is a layer comprising primarily polypropylene, B1 is a layer comprising primarily polypropylene and up to 50% by weight of a hydrocarbon resin, and B2 is a layer comprising primarily IMPEDE® polymer, and wherein the two layers in the bilayer stack are contiguous and adjacent to each other.

[0076] In one embodiment, a polymer film structure including only one two-layer PP stack does not include any other non-PP layers interspersed within the stack. Thus, for example, in an AB stack, a third non-PP layer, such as C, cannot be interspersed between A and B. However, in an A1-B-A2 stack, at least one pair of A1-B and B-A2 does not have an additional layer C disposed between them. In other words, in this embodiment, one or more AB layers do not have an interspersed C layer. Similarly, in an A1-B1-A2-B2-A3-A4 stack, at least one pair of A1 and B1, B1 and A2, A2 and B2, B2 and A3, or A3 and A4 may not have an interspersed layer C between them. In other words, in this stack, A1 is in planar contact with B1, B1 is in planar contact with A1 and A2, A2 is in planar contact with B1 and B2, and so on. In this embodiment, A represents polypropylene, B represents Impede® polypropylene, or a layer comprising primarily polypropylene and up to 50% by weight of a hydrocarbon resin, where A1, A2, etc. are different grades of polypropylene, or blends of two or more grades of polypropylene, and B1, B2, etc. are different grades of Impede® polypropylene, or blends of two or more grades of Impede®, or a layer comprising primarily polypropylene and up to 50% by weight of a hydrocarbon resin, or mixtures of different grades thereof, or mixtures thereof with Impede®.

[0077] In one embodiment, the PP stack does not include any other non-PP layers interspersed within the stack. Thus, for example, in an AB stack, a third non-PP layer, e.g., C, cannot be interspersed between A and B. Similarly, in an A1-B-A2 stack, an additional layer C cannot be disposed between A1 and B or B and A2. Similarly, in an A1-B1-A2-B2-A3-A4 stack, no layer C can be interspersed between A1 and B1, B1 and A2, A2 and B2, B2 and A3, or A3 and A4. Stated another way, in this stack, A1 is in planar contact with B1, B1 is in planar contact with A1 and A2, A2 is in planar contact with B1 and B2, and so on. In this embodiment, A represents polypropylene, B represents Impede® polypropylene, or a layer comprising primarily polypropylene and up to 50% by weight of a hydrocarbon resin, where A1, A2, etc. are different grades of polypropylene, or blends of two or more grades of polypropylene, and B1, B2, etc. are different grades of Impede® polypropylene, blends of two or more grades of Impede®, a layer comprising primarily polypropylene and up to 50% by weight of a hydrocarbon resin, mixtures of different grades thereof, or mixtures thereof with Impede®.

[0078] In one embodiment, the number of layers in the polypropylene stack ranges from 2 to 20. Stated another way, the PP stack can have any one of the following numbers of layers: 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20. In one embodiment, the number of layers in the PP stack is selected by any number within the range defined by any two numbers herein.

[0079] The present invention also contemplates rigid coextruded films comprising one or more polypropylene stacks.

[0080] In one embodiment, the rigid coextruded film of the present invention comprising at least one PP stack further comprises other layers, such that the layers are symmetrically or asymmetrically coextruded.

[0081] In one embodiment, the rigid coextruded film of the present invention comprising at least one PP stack further comprises one or more of the following layers: (1) at least one layer comprising primarily polypropylene; (2) at least one layer comprising primarily IMPEDE® or a layer comprising primarily polypropylene and up to 50% by weight of a hydrocarbon resin; (3) at least one bonding layer; (4) at least one layer comprising predominantly a polyethylene polymer or interpolymer; (5) at least one barrier layer comprising primarily EVOH; (6) at least one barrier layer comprising primarily nylon; (7) at least one barrier layer comprising primarily polyester; and (8) A combination of the above layers.

[0082] In one embodiment, the present invention relates to a polymeric film structure comprising a PP stack acting as a barrier layer, the PP stack comprising a polymeric material comprising up to about 60% by weight of at least one other polyolefin polymer and up to 50% by weight of a hydrocarbon resin. The inventors have discovered that such a polymeric film structure can exhibit unexpected improvements in certain mechanical properties while also exhibiting favorable water vapor and oxygen permeability characteristics and favorable transparency. This unexpected combination of properties, as described herein, can enable the use of such a polymeric film structure and the resulting molded polymeric article for certain packaging applications, such as those requiring extended shelf life, high wall stiffness, and / or excellent clarity. While a PP stack is obviously included in the polymeric film structure of the present invention, one or more other barrier layers, such as an EVOH layer, are also contemplated within the scope of the present invention, as described below.

[0083] II.A. Deflection temperature under load In one embodiment, the polymer film structure and / or barrier layer and / or polymer material as disclosed herein may exhibit improved performance at higher temperatures. For example, the temperature at which deformation occurs under a particular load, as indicated by the deflection temperature under load (DTUL), may be relatively high. In this regard, the DTUL may be 30°C or higher, such as 40°C or higher, for example 45°C or higher, for example 50°C or higher, for example 60°C or higher, for example 70°C or higher, for example 80°C or higher, for example 90°C or higher, for example 100°C or higher, for example 110°C or higher, for example 125°C or higher. The DTUL may be 130°C or lower, for example 120°C or lower, for example 110°C or lower, for example 100°C or lower, for example 90°C or lower, for example 80°C or lower, for example 75°C or lower. The aforementioned properties may apply to the polymer substrate, barrier layer, and / or polymer material as disclosed herein.

[0084] DTUL, in units expressed as ° C., may be the following value or within a range formed by any two of the following values ​​(including the endpoints of such range): 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, and 130.

[0085] The aforementioned properties may apply to the polymeric film structures, barrier layers, and / or polymeric materials as disclosed herein.

[0086] II.B. Tensile Modulus In one embodiment, the polymeric film structure and / or barrier layer and / or polymeric material as disclosed herein may also exhibit a relatively high tensile modulus (which is generally an indicator of stiffness). In this regard, the tensile modulus may be 500 MPa or more, such as 600 MPa or more, for example 700 MPa or more, for example 750 MPa or more, such as 800 MPa or more, for example 900 MPa or more, such as 1,000 MPa or more, for example 1,250 MPa or more, such as 1,500 MPa or more, for example 2,000 MPa or more, such as 2,250 MPa or more, for example 2,500 MPa or more, such as 2,750 MPa or more, for example 3,000 MPa or more, for example 3,250 MPa or more, such as 3,500 MPa or more, for example 4,000 MPa or more. The tensile modulus may be 5,000 MPa or less, such as 4,500 MPa or less, for example 4,000 MPa or less, for example 3,750 MPa or less, such as 3,500 MPa or less, for example 3,000 MPa or less, such as 2,500 MPa or less, for example 2,000 MPa or less, for example 1,500 MPa or less, for example 1,000 MPa or less. Further, the tensile modulus may be, expressed in MPa, the following value, or within a range formed by any two of the following values ​​(inclusive of the endpoints of such range): 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, 1000, 1050, 1100, 1150, 1200, 1250, 1300, 1350, 1400, 1450, 1500, 1550, 1600, 1650, 1700, 1750, 1800, 1850, 900, 1950, 2000, 2050, 2100, 2150, 2200, 2250, 2300, 2350, 2400, 2450, 2500, 2550, 2600, 2650, 2700, 2750, 2800 , 2850, 2900, 2950, ​​3000, 3050, 3100, 3150, 3200, 3250, 3300, 3350, 3400, 3450, 3500, 3550, 3600, 3650, 3700, 3750, 3800, 3850, 3900, 3950, 4000, 4050, 4100, 4150, 4200, 4250, 4300, 4350, 4400, 4450, 4500, 4550, 4600, 4650, 4700, 4750, 4800, 4850, 4900, 4950, and 5000.

[0087] The aforementioned properties may apply to the polymeric film structures, barrier layers, and / or polymeric materials as disclosed herein.

[0088] II.C. Yield Tensile Strength In one embodiment, the polymer film structure and / or barrier layer and / or polymer material as disclosed herein may exhibit a relatively high yield tensile strength. For example, the yield tensile strength may be 20 MPa or more, such as 25 MPa or more, such as 30 MPa or more, such as 35 MPa or more, such as 40 MPa or more, such as 45 MPa or more. The yield tensile strength may be 200 MPa or less, such as 150 MPa or less, such as 100 MPa or less, such as 90 MPa or less, such as 80 MPa or less, such as 70 MPa or less, such as 60 MPa or less, such as 50 MPa or less, such as 45 MPa or less. The yield tensile strength, expressed in MPa, may be the following value or within a range formed by any two of the following values ​​(including the endpoints of such range): 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, and 200.

[0089] The aforementioned properties may apply to the polymeric film structures, barrier layers, and / or polymeric materials as disclosed herein.

[0090] II.D. Yield Elongation In one embodiment, the polymer film structure and / or barrier layer and / or polymer material as disclosed herein may exhibit a particular yield elongation. For example, the yield elongation may be 10% or less, such as 8% or less, such as 6% or less, such as 5% or less, such as 4% or less, such as 3% or less, such as 2.5% or less, such as 2% or less, or such as 1.5% or less. The yield elongation may be 0.01% or more, such as 0.05% or more, such as 0.1% or more, such as 0.3% or more, such as 0.5% or more, such as 0.8% or more, such as 1% or more, such as 1.3% or more, such as 1.5% or more, such as 1.8% or more, such as 2% or more, such as 2.2% or more, or such as 2.4% or more. The yield elongation may also be, in %, within the following values ​​or within a range formed by any two of the following values ​​(including the endpoints of such range): 0.01, 0.03, 0.05, 0.07, 0.09, 0.1, 0.3, 0.5, 0.7, 0.9, 1.0, 1.2, 1.4, 1.6, 1.8, 2.0, 2.2, 2.4, 2.6, 2.8, 3.0, 3.2, 3.4, 3.6, 3.8, 4.0, 4.2, 4.4, 4.6, 4.8, 5.0, 5.2, 5.4, 5.6, 5.8, 6.0, 6.2, 6.4, 6.6, 6.8, 7.0, 7.2, 7.4, 7.6, 7.8, 8.0, 8.2, 8.4, 8.6, 8.8, 9.0, 9.2, 9.4, 9.6, 9.8, and 10.0.

[0091] The aforementioned properties may apply to the polymeric film structures, barrier layers, and / or polymeric materials as disclosed herein.

[0092] II.E. Flexural Properties In addition to tensile properties, the polymer film structure and / or barrier layer and / or polymer material as disclosed herein may also exhibit desirable flexural properties. For example, the flexural tangent modulus may be 500 MPa or more, such as 800 MPa or more, for example 1,000 MPa or more, for example 1,250 MPa or more, for example 1,500 MPa or more, for example 2,000 MPa or more, for example 2,250 MPa or more, for example 2,500 MPa or more, for example 2,750 MPa or more, for example 3,000 MPa or more, for example 3,250 MPa or more, for example 3,500 MPa or more, for example 4,000 MPa or more. The flexural tangent modulus may be 5,000 MPa or less, such as 4,500 MPa or less, for example 4,000 MPa or less, for example 3,750 MPa or less, such as 3,500 MPa or less, for example 3,000 MPa or less, such as 2,500 MPa or less, for example 2,000 MPa or less, for example 1,500 MPa or less, for example 1,000 MPa or less. The flexural tangent modulus may also be, expressed in MPa, the following value, or within a range formed by any two of the following values ​​(inclusive of the endpoints of such range): 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, 1000, 1050, 1100, 1150, 1200, 1250, 1300, 1350, 1400, 1450, 1500, 1550, 1600, 1650, 1700, 1750, 1800, 1850, 900, 1950, 2000, 2050, 2100, 2150, 2200, 2250, 2300, 2350, 2400, 2450, 2500, 2550, 2600, 2650, 2700, 2750, 2800 , 2850, 2900, 2950, ​​3000, 3050, 3100, 3150, 3200, 3250, 3300, 3350, 3400, 3450, 3500, 3550, 3600, 3650, 3700, 3750, 3800, 3850, 3900, 3950, 4000, 4050, 4100, 4150, 4200, 4250, 4300, 4350, 4400, 4450, 4500, 4550, 4600, 4650, 4700, 4750, 4800, 4850, 4900, 4950, and 5000.

[0093] The aforementioned properties may apply to the polymeric film structures, barrier layers, and / or polymeric materials as disclosed herein.

[0094] The polymeric film structure and / or barrier layer and / or polymeric material as disclosed herein may have a particular secant modulus, which may be 500 MPa or more, such as 800 MPa or more, for example 1,000 MPa or more, for example 1,250 MPa or more, for example 1,500 MPa or more, for example 2,000 MPa or more, for example 2,250 MPa or more, for example 2,500 MPa or more, for example 2,750 MPa or more, for example 3,000 MPa or more, for example 3,250 MPa or more, for example 3,500 MPa or more, such as 4,000 MPa or more. The flexural secant modulus may be 5,000 MPa or less, such as 4,500 MPa or less, for example 4,000 MPa or less, for example 3,750 MPa or less, such as 3,500 MPa or less, for example 3,000 MPa or less, such as 2,500 MPa or less, for example 2,000 MPa or less, for example 1,500 MPa or less, for example 1,000 MPa or less. The flexural secant modulus may also be, expressed in MPa, the following value, or within a range formed by any two of the following values ​​(inclusive of the endpoints of such range): 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, 1000, 1050, 1100, 1150, 1200, 1250, 1300, 1350, 1400, 1450, 1500, 1550, 1600, 1650, 1700, 1750, 1800, 1850, 900, 1950, 2000, 2050, 2100, 2150, 2200, 2250, 2300, 2350, 2400, 2450, 2500, 2550, 2600, 2650, 2700, 2750, 2800 , 2850, 2900, 2950, ​​3000, 3050, 3100, 3150, 3200, 3250, 3300, 3350, 3400, 3450, 3500, 3550, 3600, 3650, 3700, 3750, 3800, 3850, 3900, 3950, 4000, 4050, 4100, 4150, 4200, 4250, 4300, 4350, 4400, 4450, 4500, 4550, 4600, 4650, 4700, 4750, 4800, 4850, 4900, 4950, and 5000.

[0095] The aforementioned properties may apply to the polymeric film structures, barrier layers, and / or polymeric materials as disclosed herein.

[0096] II.F. Impact Strength The polymer film structure and / or barrier layer and / or polymer material as disclosed herein may exhibit a particular impact strength. For example, the notched Izod, e.g., notched Izod impact strength, may be 0.1 J / m or more, such as 0.5 J / m or more, such as 1 J / m or more, for example 2 J / m or more, for example 5 J / m or more, for example 8 J / m or more, for example 10 J / m or more. The notched Izod impact strength may also be 50 J / m or less, such as 40 J / m or less, for example 30 J / m or less, for example 25 J / m or less, for example 20 J / m or less, for example 18 J / m or less, for example 15 J / m or less, for example 13 J / m or less, for example 10 J / m or less. The impact strength at 23°C, expressed in units of J / m, may also be the following value or within a range formed by any two of the following values ​​(including the endpoints of such range): 0.1, 0.2, 0.5, 0.7, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, and 50.

[0097] Additionally, the Gardner impact strength may be 0.01 J or greater, such as 0.1 J or greater, for example 0.2 J or greater, such as 0.3 J or greater, for example 0.5 J or greater, such as 0.7 J or greater, for example 0.8 J or greater, such as 1 J or greater. The Gardner impact strength at 23° C., in units expressed as J / m, may also be the following value, or within a range formed by any two of the following values ​​(inclusive of the endpoints of such range): 0.01, 0.03, 0.05, 0.07, 0.09, 0.1, 0.3, 0.5, 0.7, 0.9, 1.0, 1.2, 1.4, 1.6, 1.8, 2.0, 2.2, 2.4, 2.6, 2.8, 3.0, 3.2, 3.4, 3.6, 3.8, 4.0, 4.2, 4.4, 4.6, 4.8, 5.0, 5.2, 5.4, 5.6, 5.8, 6.0, 6.2, 6.4, 6.6, 6.8, 7.0, 7.2, 7.4, 7.6, 7.8, 8.0, 8.2, 8.4, 8.6, 8.8, 9.0, 9.2, 9.4, 9.6, 9.8, and 10.0.

[0098] The aforementioned properties may apply to the polymeric film structures, barrier layers, and / or polymeric materials as disclosed herein.

[0099] II.G. Melt Flow Rate The polymeric material as disclosed herein may have a specific melt flow rate. For example, the melt flow rate may be 1 g / 10 min or more, for example, 2 g / 10 min or more, for example, 2.2 g / 10 min or more, for example, 2.5 g / 10 min or more, for example, 3 g / 10 min or more, for example, 3.5 g / 10 min or more, for example, 4 g / 10 min or more, for example, 4.5 g / 10 min or more, for example, 5 g / 10 min or more, for example, 10 g / 10 min or more, for example, 15 g / 10 min or more, for example, 20 g / 10 min or more, for example, 30 g / 10 min or more. The melt flow rate may be 100 g / 10 min or less, for example 80 g / 10 min or less, for example 60 g / 10 min or less, for example 50 g / 10 min or less, for example 40 g / 10 min or less, for example 30 g / 10 min or less, for example 20 g / 10 min or less, for example 15 g / 10 min or less, for example 11 g / 10 min or less, for example 10 g / 10 min or less, for example 9 g / 10 min or less, for example 8 g / 10 min or less, for example 7.5 g / 10 min or less, for example 7 g / 10 min or less, for example 6.5 g / 10 min or less, for example 6 g / 10 min or less. The melt flow rate, expressed in g / 10 min, may be the following value, or within a range formed by any two of the following values ​​(including the endpoints of such range): 1, 1.2, 1.5, 2, 2.2, 2.5, 3, 3.2, 3.5, 4, 4.2, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, and 100.

[0100] II.H. Haze and Clarity Also important for various applications are the optical properties of the polymer film structure, barrier layer, and / or polymer material, particularly transparency and / or haze. For example, it may be desirable to have a low haze. Even with certain additives and a relatively thick film, the percent haze may be 60 or less, such as 50 or less, for example 40 or less, for example 30 or less, for example 20 or less, for example 18 or less, for example 16 or less, for example 14 or less, for example 12 or less, for example 10 or less, for example 8 or less, for example 6 or less, for example 5 or less, for example 4 or less. The percent haze may be 0 or more, for example 1 or more, for example 2 or more, for example 3 or more, for example 4 or more, for example 5 or more, for example 10 or more, for example 25 or more. In addition, the percent transparency may be 90 or more, for example 95 or more, for example 96 or more, for example 97 or more, for example 98 or more, for example 99 or more.

[0101] With certain additives, even at relatively high thicknesses, the percent haze can be the following value, or within the range formed by any two of the following values, inclusive of the endpoints of such ranges: 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, and 60.

[0102] Additionally, the percent transparency can be the following value, or within a range formed by any two of the following values, inclusive of the endpoints of such range: 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, and 100.

[0103] The aforementioned properties may apply to polymeric film structures, barrier layers, and / or polymeric materials as disclosed herein. Additionally, such properties may be achieved at a single thickness value or within a range of thicknesses as disclosed herein. For example, percent haze or clarity may be for a polymeric material when formed at a particular thickness (e.g., 25 mils and / or 50 mils). Percent haze and clarity may be determined according to ASTM D1003.

[0104] II.I. Transmission characteristics In addition to desirable mechanical and optical properties, the polymer film structures and / or barrier layers and / or polymer materials disclosed herein may also exhibit relatively low permeability. Such permeability may allow the polymer film structures and / or barrier layers and / or polymer materials to be utilized in various packaging applications. In this regard, the polymer film structures and / or barrier layers and / or polymer materials may exhibit relatively low water vapor and / or oxygen permeability. For example, the water vapor permeability may be 5 cm 3 / m 2 / day or less, e.g., 4 cm 3 / m 2 / day or less, e.g., 3 cm 3 / m 2 / day or less, e.g., 2 cm 3 / m 2 / day or less, e.g., 1 cm 3 / m 2 / day or less, e.g., 0.5 cm 3 / m 2 / day or less, e.g., 0.1 cm 3 / m 2 / day or less, e.g., 0.08 cm 3 / m 2 / day or less, e.g., 0.06 cm 3 / m 2 / day or less, e.g., 0.05 cm 3 / m 2 / day or less, e.g., 0.03 cm 3 / m 2 / day or less, e.g., 0.01 cm 3 / m 2 / day or less, e.g., 0.005 cm3 / m 2 / day or less, e.g., 0.001 cm 3 / m 2 / day or less. The water vapor transmission rate is 0 cm 3 / m 2 / day, e.g., 0.001 cm 3 / m 2 / day or more, e.g., 0.005 cm 3 / m 2 / day or more, e.g., 0.01 cm 3 / m 2 / day or more, e.g., 0.05 cm 3 / m 2 / day or more, e.g., 0.1 cm 3 / m 2 / day or more. Water vapor transmission rate is also expressed in cm 3 / m 2 / day, may be within the following values ​​or within the range formed by any two of the following values ​​(including the endpoints of such ranges): 0, 0.0005, 0.001, 0.005, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, and 5.

[0105] In addition, the oxygen permeability is 60cm 3 / 100in 2 / day or less, e.g., 50 cm 3 / 100in 2 / day or less, e.g., 40 cm 3 / 100in 2 / day or less, e.g. 30cm 3 / 100in 2 / day or less, e.g. 25cm 3 / 100in 2 / day or less, e.g., 20 cm 3 / 100in 2 / day or less, e.g. 15cm 3 / 100in 2 / day or less, e.g., 10 cm 3 / 100in 2 / day or less, e.g., 5 cm 3 / 100in 2 / day or less, e.g., 4 cm 3 / 100in 2 / day or less, e.g., 3 cm 3 / 100in 2 / day or less, e.g., 2.5 cm 3 / 100in 2 / day or less. Oxygen permeability is 0 cm 3 / 100in 2 / day, e.g., 0.5 cm 3 / 100in 2 / day or more, e.g., 1 cm 3 / 100in 2 / day or more, e.g., 3 cm 3 / 100in 2 / day or more, e.g., 5 cm 3 / 100in 2 / day or more, e.g., 8 cm 3 / 100in 2 / day or more, e.g., 10 cm 3 / 100in 2 / day or more. The oxygen permeability may be for the polymeric material when formed at a particular thickness (e.g., 8 mils, 10 mils, and / or 18 mils). The oxygen permeability may also be measured in cm 3 / 100in 2 / day, may be within the following values ​​or within the range formed by any two of the following values ​​(including the endpoints of such ranges): 0, 0.1, 0.2, 0.3, 0.4, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, and 60.

[0106] The oxygen permeability can be for a polymeric material when formed at a particular thickness (eg, 8 mils, 10 mils, and / or 18 mils).

[0107] II.J. Polymer Film Structure Thickness For example, the polymer film structure may have a thickness of more than 200 μm, such as 210 μm or more, for example 220 μm or more, such as 240 μm or more, for example 250 μm or more, such as 300 μm or more, for example 350 μm or more, such as 400 μm or more, for example 500 μm or more, such as 700 μm or more, for example 900 μm or more, such as 1 mm or more, for example 2 mm or more, such as 3 mm or more, for example 5 mm or more. The polymer film structure may have a thickness of 1.25 cm or less, such as 1 cm or less, for example 8 mm or less, such as 5 mm or less, for example 3 mm or less, such as 2 mm or less, for example 1.5 mm or less, such as 1.3 mm or less, for example 1 mm or less, such as 900 μm or less, for example 800 μm or less, such as 700 μm or less, for example 600 μm or less, such as 500 μm or less, for example 400 μm or less, such as 350 μm or less, for example 300 μm or less, such as 280 μm or less, for example 270 μm or less.

[0108] Alternatively stated, the thickness of the polymer film structure, in μm, can be any number below, or within a range defined by any two numbers below, inclusive of the endpoints of such ranges. 5, 10, 20, 30, 50, 50, 75, 100, 125, 150, 175, 200, 225, 250, 275, 300, 325, 350, 375, 400, 425, 450, 475, 500, 525, 550, 575, 600, 625, 650, 675, 700, 725, 750, 775, 800, 825, 850, 875, 900, 925, 950, 975, 1000, 1025, 1050, 1100, 1125, 1150, 1175, 1200, 1225, 1250, 1275, 1300, 1325, 1350, 1375, 1400, 1425, 1450, 1475, 1500, 1525, 1600, 1700, 1800, 1900, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 6000, 7000, 8000, 9000, 10000, 11000, 12000 and 13000.

[0109] The aforementioned properties may apply to the barrier layer. In addition, if the polymer film structure is a single layer polymer film structure that simply includes a barrier layer as defined herein, the aforementioned thicknesses may also apply to the barrier layer.

[0110] In one embodiment, the present invention also relates to a laminate structure prepared from the polymer film structure described above. For example, in one embodiment, the present invention relates to a laminate structure comprising the coextruded structure described herein, which comprises at least one polypropylene stack. Such laminations include extrusion lamination, thermal lamination, and / or adhesive lamination (solvent and solvent-free). In other words, while the polypropylene stack is coextruded, the laminate structure comprising the PP stack may have some or all of the other layers coextruded (non-PP stack layers), some or all of the other layers thermally laminated, some or all of the other layers adhesively laminated (solvent and solvent-free), and / or some or all of the other layers prepared by a different method, such as printing, forming / molding, etc. Such laminations can be used to construct thicker laminate structures. In other words, the thickness of the laminate structure, in μm, can be any of the following values, or within a range defined by any two of the following values ​​(including the endpoints of such range): 5, 10, 20, 30, 50, 50, 75, 100, 125, 150, 175, 200, 225, 250, 275, 300, 325, 350, 375, 400, 425, 450, 475, 500, 525, 550, 575, 600, 625, 650, 675, 700, 725, 750, 775, 800, 825, 850, 875, 900, 925, 950, 975, 1000, 1025, 1050, 1100, 1125, 1150, 1175, 1200, 1225, 1250, 1275, 1300, 1325, 1350, 1375, 1400, 1425, 1450, 1475, 1500, 1525, 1600, 1700, 1800, 1900, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 6000, 7000, 8000, 9000, 10000, 11000, 12000 and 13000.

[0111] In one embodiment, such laminate structures are rigid sheets ranging in thickness from 10 μm to 1525 μm (0.5 mils to 60 mils).

[0112] The present invention also includes making polymeric film structures using other forming techniques besides lamination, such as printing, forming, and molding.

[0113] The present invention also contemplates polymeric film structures as disclosed above, wherein the film structure is flexible, semi-rigid, or rigid. As contemplated within the scope of the present invention, stiffness generally correlates to the thickness of the polymeric film structure, although this need not necessarily be the case.

[0114] In one embodiment, in a layer that primarily comprises polypropylene, other components in the layer include polyolefins, hydrocarbon resins, and optionally additives. The polypropylene, polyolefins, hydrocarbons, and other materials are described herein. One or more outer layers of the PP stack of the polymer film structure herein include other materials described herein and other materials in the art. The other layers are not primarily PP.

[0115] III. Materials for Polymer Film Structures III.A. Polypropylene The general material properties of PP are listed below. ●Density 0.88~0.93g / cm 3 ●Melt index 0.30~10g / 10min ●Embrittlement temperature <-20℃ ●Maximum continuous use temperature: 82°C (180°F) Deflection temperature under load: 115°C (240°F)

[0116] In the present invention, the polypropylene (PP) in a coextruded layer within a PP stack or other film may be a homopolymer polypropylene, a homogeneous copolymer of polypropylene, a heterogeneous copolymer of polypropylene, or a blend of a polypropylene copolymer and a polypropylene homopolymer. The PP content of the polypropylene layer within the PP stack or other rigid film is in the range of about 40 to about 100 parts by weight. In other words, in the polypropylene layer, the PP content is one of the following values, expressed as a weight percent of the polypropylene layer: 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, and 100.

[0117] The PP content can also be within a range defined by any two numbers above, inclusive of the range endpoints.

[0118] In one embodiment, to prepare a high impact strength version of the film, the grade of polypropylene or polypropylene blend used is such that the Izod impact strength of the PP exceeds 9 ft-lbf per inch notch according to American Society for Testing and Materials (ASTM) standard D256.

[0119] More preferably, a particularly suitable polypropylene may be a blown film-grade, high-impact copolymer having an Izod impact strength (ASTM D 257, 23°C) of 8 to 80 ft-lbf per notch inch and a melt flow index (ASTM D 1238, 2.16 kg, 23°C) of about 0.3 to about 5.5 dg / min (or g / 10 min). The Izod impact strength range can also be defined by any two numbers from 8, 9, 10, ..., 78, 79, and 80 ft-lbf per notch inch. Similarly, the melt flow index range can also be defined by any two numbers from about 0.3, about 0.35, about 0.4, about 0.45, ..., about 5.40, about 5.45, and about 5.50 dg / min. In a preferred embodiment, the at least one polypropylene has a melt index in the range of about 0.45 to about 0.75 dg / min.

[0120] The polypropylene used in the present invention may also be polymerized using a Ziegler-Natta catalyst, or a single-site catalyst, or a combination of these catalysts.

[0121] Isotactic polypropylene homopolymer ("homoPP") is a uniform polymer that is typically polymerized in a single-stage reaction and has a single, distinct DSC melting peak in the 160-165°C region.

[0122] Homogeneous polypropylene also consists of a single phase and has a single, distinct DSC melting peak, which occurs at a lower temperature than that of the homopolymer. The melting energy of homogeneous interpolymers is also somewhat lower than that of the homopolymer.

[0123] Heterogeneous polypropylene is formed in a two-stage reaction. In the first stage, a crystalline network of isotactic polypropylene homopolymer or homogeneous polypropylene is formed. In the second stage, a largely amorphous rubber phase forms within the crystalline network. A portion of the polymer formed in the second stage reaction is usually sufficiently rich in comonomer that it can crystallize to form a third phase. When the comonomer is ethylene, the third phase typically has a DSC melting peak in the 120-125°C region.

[0124] III.B. IMPEDE® Polypropylene IMPEDE® Polypropylene means a polypropylene homopolymer having the following properties: It is sourced from Flint Hills Resources, 8128 Up River Road, Corpus Christi, TX 78410. It has been clarified with Impede reinforcement technology, which provides higher stiffness, improved barrier (O2 and H2O), and high clarity.

[0125] [Table 1]

[0126] [Table 2]

[0127] III.C. Polyolefins The polymer film structure of the present invention may comprise one or more layers comprising at least one polyolefin. Even a PP stack layer (mainly comprising polypropylene) may further comprise at least one other polyolefin.

[0128] The polyolefin polymer may be formed from an olefin monomer, such as an α-olefin monomer. In this regard, the monomer may be ethylene, such that the polyolefin polymer comprises an ethylene polymer. Additionally, the monomer may be propylene, such that the polyolefin polymer comprises a propylene polymer. In one particular embodiment, the polyolefin polymer comprises a propylene polymer.

[0129] In general, polyolefin polymers can be homopolymers or copolymers. In one embodiment, the polyolefin polymer comprises a homopolymer. For example, when the polyolefin polymer comprises a propylene polymer, such polymer can be a propylene homopolymer. In another embodiment, the polyolefin polymer comprises a copolymer. For example, when the polyolefin polymer comprises a propylene polymer, such polymer can be a propylene copolymer. Thus, in one embodiment, the propylene polymer can be a propylene homopolymer. In another embodiment, the propylene polymer can be a propylene copolymer. In particular, the propylene copolymer can be a propylene elastomer.

[0130] Similarly, when the polyolefin polymer comprises a homopolymer and the polyolefin polymer comprises an ethylene polymer, such polymer may be an ethylene homopolymer. In another embodiment, when the polyolefin polymer comprises a copolymer and the polyolefin polymer comprises an ethylene polymer, such polymer may be an ethylene copolymer. Thus, in one embodiment, the ethylene polymer may be an ethylene homopolymer. In another embodiment, the ethylene polymer may be an ethylene copolymer. In particular, the ethylene copolymer may be an ethylene elastomer.

[0131] When present as a copolymer, the copolymer may include at least one comonomer comprising at least one α-olefin (i.e., other than ethylene in the case of an ethylene copolymer, or other than propylene in the case of a propylene copolymer). In this regard, the comonomer may be ethylene (in the case of a propylene copolymer), propylene (in the case of an ethylene copolymer), C4-C6 20 For example, the comonomer may comprise a C4 to C6 α-olefin, an α-olefin, or a combination thereof. 20 When including an α-olefin, the comonomer may, in certain embodiments, be a C4-C 12 α-olefins, e.g., C4-C 10 The α-olefin may be, for example, a C4 to C8 α-olefin. In any case, specific examples of the α-olefin include, but are not limited to, ethylene, butene (e.g., 1-butene, 3-methyl-1-butene, 3,3-dimethyl-1-butene), pentene (e.g., 4-methyl-1-pentene, 3-methyl-1-pentene), hexene (e.g., 1-hexene, 3,5,5-trimethyl-1-hexene), heptene, octene (e.g., 1-octene, 2-octene), nonene (e.g., 5-methyl-1-nonene), decene, dodecene, and styrene.

[0132] In certain embodiments, the comonomer may include at least one of ethylene (for propylene copolymers), propylene (for ethylene copolymers), 1-butene, 1-hexene, or 1-octene. For example, in one embodiment, the comonomer may include at least ethylene (for propylene copolymers) or propylene (for ethylene copolymers). In another embodiment, the comonomer may include at least ethylene and at least one of 1-butene, 1-hexene, or 1-octene.

[0133] In addition, it should be understood that suitable α-olefins can be straight-chained or branched-chained (e.g., one or more C1-C3 alkyl branched-chain or aryl groups). For example, in one embodiment, the α-olefin can be straight-chained. In another embodiment, the α-olefin can be branched-chained. In this regard, the α-olefin can be substituted, such as with one or more methyl, dimethyl, trimethyl, ethyl, or propyl substituents. However, it should also be understood that the α-olefin can be unsubstituted.

[0134] In addition to the above-mentioned α-olefin comonomers, the copolymers may optionally contain other comonomers. For example, these comonomers may include aromatic group-containing comonomers, non-aromatic cyclic group-containing comonomers, and / or diolefin comonomers. For example, these comonomers may contain 4 or more, such as 5 or more, such as 8 or more, such as 10 or more, such as 15 or more, carbon atoms to 30 or less, such as 25 or less, such as 20 or less, such as 15 or less, such as 10 or less, carbon atoms.

[0135] In one embodiment, the comonomer may comprise a diene. The diene may be a linear acyclic olefin, a branched acyclic olefin, a single-ring alicyclic olefin, a multi-ring alicyclic fused or bridged olefin, a cycloalkenyl-substituted alkene, or a mixture thereof. Examples of the diene include butadiene, pentadiene, hexadienes (e.g., 1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,4-cyclohexadiene), heptadiene (e.g., 1,6-heptadiene), octadiene (e.g., 1,6-octadiene, 1,7-octadiene, 3,7-dimethyl-1,6-octadiene, 3,7-dimethyl-1,7-octadiene, 1,5-cyclooctadiene), nonadienes (e.g., 1,8-nonadiene), decadienes (e.g., 1,8-diene), and the like. 9-decadiene), undecadiene (e.g., 1,10-undecadiene), dodecadiene (e.g., 1,11-dodecadiene, 1,7-cyclododecadiene), tridecadiene (e.g., 1,12-tridecadiene), tetradecadiene (e.g., 1,13-tetradecadiene), pentadecadiene, hexadecadiene, heptadecadiene, octadecadiene, nonadecadiene, icosadiene, heneicosadiene, docosadiene, tricosadiene, tetracosadiene, pentacosadiene , hexacosadiene, heptacosadiene, octacosadiene, nonacosadiene, triacontadiene, tetrahydroindene, norbornadiene, methyl-tetrahydroindene, dicyclopentadiene, bicyclo-(2.2.1)-hepta-2,5-diene, alkenylnorbornenes, alkylidenenorbornenes (e.g., ethylidenenorbornene), cycloalkenylnorbornenes, cycloalkylenenorbornenes (e.g., 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, 4-vinyl-2-norbornene, 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene, 5-(4-cyclopentenyl)-2-norbornene, 5-cyclohexylidene-2-norbornene, 5-vinyl-2-norbornene), vinylcyclohexene, allylcyclohexene, vinylcyclooctene, 4-vinylcyclohexene, allylcyclodecene, vinylcyclododecene, and tetracyclo(A-11,12)-5,8-dodecene.

[0136] The diene may also include polybutadienes, such as low molecular weight butadienes. For example, the polybutadienes may have a weight average molecular weight of about 2,000 g / mol or less, e.g., about 1,500 g / mol or less, e.g., about 1,000 g / mol or less. The diene may include cyclic dienes, such as cyclopentadiene, vinylnorbornene, norbornadiene, ethylidenenorbornene, divinylbenzene, dicyclopentadiene, or higher ring-containing diolefins, with or without substituents at various ring positions.

[0137] Regardless of the type of comonomer utilized, the primary monomer (i.e., ethylene or propylene) may comprise about 50 mol% or more of the copolymer, such as about 60 mol% or more, for example about 65 mol% or more, for example about 70 mol% or more, for example about 75 mol% or more, for example about 80 mol% or more, for example about 85 mol% or more, for example about 90 mol% or more, such as about 93 mol% or more. The primary monomer (i.e., ethylene or propylene) may comprise less than 100 mol% of the copolymer, such as about 99.5 mol% or less, for example about 99 mol% or less, for example about 98 mol% or less, such as about 97 mol% or less, for example about 95 mol% or less. Thus, the primary monomer (i.e., ethylene or propylene) may constitute about 50% by weight or more of the copolymer, such as about 60% by weight or more, for example about 65% by weight or more, such as about 70% by weight or more, for example about 75% by weight or more, such as about 80% by weight or more, for example about 85% by weight or more, such as about 90% by weight or more, for example about 93% by weight or more. The primary monomer (i.e., ethylene or propylene) may constitute less than 100% by weight of the copolymer, such as about 99.5% by weight or less, for example about 99% by weight or less, such as about 98% by weight or less, for example about 97% by weight or less, for example about 95% by weight or less.

[0138] Similarly, a comonomer such as an α-olefin may constitute about 0.1 mol% or more of the copolymer, for example, about 0.3 mol% or more, for example, about 0.5 mol% or more, for example, about 1 mol% or more, for example, about 2 mol% or more, for example, about 3 mol% or more, for example, about 5 mol% or more. The comonomer may constitute less than 50 mol%, for example, about 40 mol% or less, for example, about 35 mol% or less, for example, about 30 mol% or less, for example, about 20 mol% or less, for example, about 15 mol% or less, for example, about 10 mol% or less, for example, about 7 mol% or less. Thus, the comonomer may constitute about 0.1 wt% or more of the copolymer, for example, about 0.3 wt% or more, for example, about 0.5 wt% or more, for example, about 1 wt% or more, for example, about 2 wt% or more, for example, about 3 wt% or more, for example, about 5 wt% or more. The comonomer may comprise less than 50 wt% of the copolymer, such as about 40 wt% or less, for example about 30 wt% or less, for example about 25 wt% or less, for example about 20 wt% or less, for example about 15 wt% or less, for example about 10 wt% or less, for example about 8 wt% or less, for example about 7 wt% or less. It should be understood that the foregoing percentages may apply to all of the comonomers in combination or to a single type of comonomer utilized in the copolymer.

[0139] In embodiments in which a third comonomer (e.g., one that does not include ethylene) is present, such third comonomer may be present in an amount of about 10% by weight or less, such as about 5% by weight or less, for example about 4% by weight or less, such as about 3% by weight or less, for example about 2% by weight or less, based on the weight of the copolymer.

[0140] In a particular embodiment, the polyolefin polymer can be a polyolefin copolymer elastomer. For example, the propylene copolymer can be a propylene copolymer elastomer. As generally understood in the art, the elastomer can meet the properties of ASTM D1566-19. In one embodiment, the elastomer can include ethylene and at least one comonomer from propylene, butene, hexene, and octene. In another embodiment, the elastomer can include propylene and at least one comonomer from ethylene, butene, hexene, and octene. In a particular embodiment, the elastomer includes propylene and ethylene. For example, the elastomer can include no additional comonomers. However, in one embodiment, the elastomer can include propylene, ethylene, and at least one of butene, hexene, and octene. For example, the elastomer can include propylene-ethylene-butene, propylene-ethylene-hexene, propylene-ethylene-octene, or mixtures thereof. In this regard, in one embodiment, the elastomer may comprise propylene-ethylene-butene. In another embodiment, the elastomer may comprise propylene-ethylene-hexene. In a further embodiment, the elastomer may comprise propylene-ethylene-octene.

[0141] In general, polyolefin copolymers can have any monomer sequence. For example, the polyolefin copolymer can be a random copolymer. Alternatively, in another embodiment, the polyolefin copolymer can be a block copolymer. In a further embodiment, the polyolefin copolymer can be a heterophasic copolymer.

[0142] Polyolefin polymers may have a particular molecular structure that may enable them to be utilized for specific applications. In this regard, the polyolefin polymer may have a degree of tacticity. For example, in one embodiment, the polyolefin polymer may be an isotactic polyolefin polymer. In particular, the polyolefin homopolymer may be an isotactic polyolefin homopolymer. In this regard, the polyolefin polymer may have an isotacticity of at least 50%, such as at least 60%, such as at least 70%, such as at least 80%, such as at least 85%, or such as at least 90%, as determined according to analysis by C-NMR.

[0143] However, it should be understood that the polyolefin polymer may alternatively have an atactic or syndiotactic molecular structure. For example, in one embodiment, the polyolefin polymer may be an atactic polyolefin polymer. In another embodiment, the polyolefin polymer may be a syndiotactic polyolefin polymer. For example, the polyolefin polymer may have a syndiotacticity of at least 50%, such as at least 60%, such as at least 70%, such as at least 80%, such as at least 85%, or such as at least 90%, as determined according to analysis by C-NMR.

[0144] Generally, polyolefin homopolymers can have a higher isotacticity or syndiotacticity and generally a lower atacticity.For example, syndiotactic polyolefin homopolymers can have a syndiotacticity of at least 80%, for example, at least 85%, for example, at least 90%.Similarly, isotactic polyolefin homopolymers can have an isotacticity of at least 80%, for example, at least 85%, for example, at least 90%.Therefore, such polyolefin homopolymers can have an atacticity of less than 20%, for example, less than 15%, for example, less than 10%, for example, less than 5%.

[0145] In this regard, polyolefin polymers can have a certain crystallinity.For example, the crystallinity can be at least about 1%, for example, at least about 2%, for example, at least about 5%, for example, at least about 10%, for example, at least about 15%, for example, at least about 20%, for example, at least about 25%, for example, at least about 30%, for example, at least about 40%, for example, at least about 50%, for example, at least about 60%, for example, at least about 70%, for example, at least about 80%, for example, at least about 90%, for example, at least about 95%, for example, at least about 98%, for example, at least about 99%.Crystallization is generally less than 100%.For example, the crystallinity can be less than 100%, for example, about 99% or less, for example, about 98% or less, for example, about 95% or less, for example, about 90% or less, for example, about 80% or less, for example, about 70% or less, for example, about 60% or less, for example, about 50% or less, for example, about 40% or less, for example, about 30% or less, for example, about 20% or less. For example, polyolefin homopolymers may generally have a higher degree of crystallinity than polyolefin copolymer elastomers.

[0146] Crystallinity can be determined based on xylene solubles. For example, higher crystallinity results in lower xylene solubles. In this regard, the xylene solubles weight percentage can be 50% or less, for example 40% or less, for example 30% or less, for example 20% or less, for example 15% or less, for example 10% or less, for example 5% or less, for example 4% or less, for example 3% or less, for example 2% or less, for example 1% or less. Without intending to be limiting, xylene solubles provides a measure of the amorphous portion of polyolefin polymer. Xylene solubles can be determined according to ASTM D5492-17.

[0147] Generally, the crystallinity of a polyolefin polymer can affect the melting temperature and crystallization temperature of the polymer. In this regard, the melting temperature and crystallization temperature of a polyolefin polymer can be relatively low. For example, the melting temperature can be about 70°C or higher, for example, about 85°C or higher, for example, about 100°C or higher, for example, about 110°C or higher, for example, about 120°C or higher, for example, about 130°C or higher, for example, about 140°C or higher, for example, about 150°C or higher, for example, about 160°C or higher, for example, about 165°C or higher. The melting temperature can be about 170°C or lower, for example, about 160°C or lower, for example, about 150°C or lower, for example, about 125°C or lower, for example, about 115°C or lower, for example, about 100°C or lower. For example, polyolefin homopolymers generally have higher melting temperatures than polyolefin copolymer elastomers.

[0148] The crystallization temperature of the polyolefin polymer may be about 70° C. or higher, such as about 80° C. or higher, for example about 90° C. or higher, such as about 95° C. or higher, for example about 100° C. or higher, such as about 105° C. or higher, for example about 110° C. or higher, such as about 115° C. or higher, for example about 120° C. or higher, such as about 125° C. The crystallization temperature may be about 140° C. or lower, such as about 130° C. or lower, for example about 120° C. or lower, such as about 110° C. or lower, for example about 100° C. or lower.

[0149] The glass transition temperature of the polyolefin polymer may be about 125° C. or less, such as about 115° C. or less, for example about 105° C. or less, such as about 100° C. or less, for example about 90° C. or less, such as about 80° C. or less, for example about 70° C. or less, such as about 50° C. or less, for example about 40° C. or less, such as about 30° C. or less, for example about 20° C. or less, such as about 10° C. or less, for example about 0° C. The glass transition temperature may be about −50° C. or more, such as about −40° C. or more, for example about −30° C. or more, such as about −20° C. or more, for example about −10° C. or more, such as about 0° C. or more, for example about 20° C. or more, such as about 40° C. or more, for example about 50° C. or more.

[0150] Polyolefin polymers may also have specific properties that may allow them to be used in specific applications. In this regard, polyolefin polymers may have a specific weight average molecular weight (Mw). For example, Mw may be about 2,500 g / mol or more, for example, about 5,000 g / mol or more, for example, about 8,000 g / mol or more, for example, about 10,000 g / mol or more, for example, about 12,000 g / mol or more, for example, about 20,000 g / mol or more, for example, about 25,000 g / mol or more, for example, about 50,000 g / mol or more, for example, about 80,000 g / mol or more, for example, about 90,000 g / mol or more, for example, about 100,000 g / mol or more, for example, about 200,000 g / mol or more, for example, about 300,000 g / mol or more. The Mw can be about 1,000,000 g / mol or less, such as about 800,000 g / mol or less, for example about 600,000 g / mol or less, for example about 500,000 g / mol or less, such as about 400,000 g / mol or less, for example about 300,000 g / mol or less, for example about 250,000 g / mol or less, such as about 200,000 g / mol or less, for example about 150,000 g / mol or less, for example about 100,000 g / mol or less, for example about 50,000 g / mol or less. Mw can be determined using techniques known in the art, such as gel permeation chromatography.

[0151] Similarly, the polyolefin polymer may also have a particular number average molecular weight (Mn). For example, Mn may be about 2,500 g / mol or more, such as about 5,000 g / mol or more, for example, about 8,000 g / mol or more, such as about 10,000 g / mol or more, for example, about 12,000 g / mol or more, such as about 20,000 g / mol or more, for example, about 25,000 g / mol or more, such as about 50,000 g / mol or more, for example, about 80,000 g / mol or more, such as about 90,000 g / mol or more, for example, about 100,000 g / mol or more, such as about 200,000 g / mol or more, for example, about 300,000 g / mol or more. Mn can be about 1,000,000 g / mol or less, such as about 800,000 g / mol or less, for example about 600,000 g / mol or less, for example about 500,000 g / mol or less, such as about 400,000 g / mol or less, for example about 300,000 g / mol or less, such as about 250,000 g / mol or less, for example about 200,000 g / mol or less, such as about 150,000 g / mol or less, for example about 100,000 g / mol or less, for example about 50,000 g / mol or less. Mn can be determined using techniques known in the art, such as gel permeation chromatography.

[0152] In this regard, the polyolefin polymer may have a particular polydispersity index (Mw / Mn). For example, the polydispersity index may be greater than 1, such as about 2 or more, such as about 2.3 or more, such as about 2.5 or more, such as about 3 or more, such as about 3.5 or more, such as about 4 or more. The polydispersity index may be about 9 or less, such as about 8 or less, such as about 7 or less, such as about 5 or less, such as about 4.5 or less, such as about 4 or less, such as about 3.5 or less, such as about 3 or less, such as about 2.5 or less.

[0153] The polyolefin polymer may have a specific gravity, for example, a specific gravity of about 0.8 g / cm 3 For example, about 0.83 g / cm 3 or more, for example, about 0.85 g / cm 3 or more, for example, about 0.86 g / cm 3 For example, about 0.87 g / cm 3For example, about 0.88 g / cm 3 or more, for example, about 0.9 g / cm 3 The specific gravity can be 1 g / cm or more. 3 less than, for example, about 0.95 g / cm 3 Below, for example, about 0.93 g / cm 3 For example, about 0.92 g / cm 3 For example, about 0.91 g / cm 3 Below, for example, about 0.9 g / cm 3 Below, for example, about 0.89 g / cm 3 Below, for example, about 0.88 g / cm 3 The specific gravity may be determined in accordance with ASTM D792-20.

[0154] The polyolefin polymer may have a specific melt flow rate. For example, the melt flow rate may be about 0.1 g / 10 min or more, for example, about 0.2 g / 10 min or more, for example, about 0.3 g / 10 min or more, for example, about 0.4 g / 10 min or more, for example, about 0.5 g / 10 min or more, for example, about 1 g / 10 min or more, for example, about 1.5 g / 10 min or more, for example, about 2 g / 10 min or more, for example, about 5 g / 10 min or more, for example, about 10 g / 10 min or more, for example, about 20 g / 10 min or more, for example, about 25 g / 10 min or more. The melt flow rate may be about 500 g / 10 min or less, such as about 200 g / 10 min or less, for example, about 100 g / 10 min or less, for example, about 50 g / 10 min or less, for example, about 40 g / 10 min or less, such as about 20 g / 10 min or less, for example, about 10 g / 10 min or less, such as about 5 g / 10 min or less, for example, about 4 g / 10 min or less, for example, about 3 g / 10 min or less, such as about 2 g / 10 min or less, for example, about 1.5 g / 10 min or less, such as about 1 g / 10 min or less, for example, about 0.8 g / 10 min or less, for example, about 0.6 g / 10 min or less, such as about 0.5 g / 10 min or less, for example, about 0.45 g / 10 min or less, for example, about 0.4 g / 10 min or less, such as about 0.35 g / 10 min or less, for example, about 0.3 g / 10 min or less. The melt flow rate may be determined according to ASTM D1238-13 at a temperature of 230° C. for 10 minutes under a load of 2.16 kg.

[0155] The polyolefin polymer may also have a specific heat of fusion. For example, the heat of fusion may be about 40 J / g or more, for example, about 50 J / g or more, for example, about 60 J / g or more, for example, about 70 J / g or more, for example, about 75 J / g or more, for example, about 80 J / g or more, for example, about 90 J / g or more, for example, about 100 J / g or more, for example, about 125 J / g or more, for example, about 150 J / g or more, for example, about 200 J / g or more. The heat of fusion may be about 300 J / g or less, for example, about 250 J / g or less, for example, about 200 J / g or less, for example, about 150 J / g or less, for example, about 125 J / g or less, for example, about 100 J / g or less, for example, about 80 J / g or less, for example, about 75 J / g or less, for example, about 70 J / g or less, for example, about 65 J / g or less, for example, about 60 J / g or less, for example, about 50 J / g or less. For example, a polyolefin homopolymer may have a relatively high heat of fusion, while a polyolefin copolymer elastomer may have a relatively low heat of fusion.

[0156] The polyolefin polymer may also have a specific crystallinity. For example, the crystallinity may be 50% or more, for example 60% or more, for example 70% or more, for example 80% or more, for example 90% or more. Generally, the percentage is used to define the weight of the crystalline region per total weight of the polymer, and can be determined using means known in the art, such as a differential scanning calorimeter or an X-ray diffractometer (XRD). In addition, the polyolefin polymer may have an isotacticity of 95% or more, for example 96% or more, for example 97% or more. Furthermore, the polyolefin polymer may have an atactic fraction of 5% or less, for example 4% or less, for example 3% or less.

[0157] The polyolefin polymer may also have a specific flexural modulus. For example, the flexural modulus in the machine direction may be about 50 MPa or more, for example, about 100 MPa or more, for example, about 200 MPa or more, for example, about 300 MPa or more, for example, about 400 MPa or more, for example, about 500 MPa or more, for example, about 1,000 MPa or more, for example, about 1,300 MPa or more, for example, about 1,500 MPa or more, for example, about 2,000 MPa or more. The flexural modulus in the machine direction may be about 4,000 MPa or less, for example, about 3,000 MPa or less, for example, about 2,500 MPa or less, for example, about 2,300 MPa or less, for example, about 2,100 MPa or less, for example, about 2,000 MPa or less, for example, about 1,900 MPa or less, for example, about 1,800 MPa or less, for example, about 1,500 MPa or less, for example, about 1,300 MPa or less, for example, about 1,000 MPa or less, for example, about 800 MPa or less. Flexural modulus may be determined according to ASTM D790-17 and 1.3 mm / min.

[0158] The polyolefin polymer may also have a specific deflection temperature under load (DTUL). For example, the DTUL may be about 40°C or higher, such as about 45°C or higher, for example, about 50°C or higher, for example, about 60°C or higher, for example, about 70°C or higher, for example, about 80°C or higher. The DTUL may be about 130°C or lower, for example, about 120°C or lower, for example, about 110°C or lower, for example, about 100°C or lower, for example, about 90°C or lower, for example, about 80°C or lower, for example, about 75°C or lower. The DTUL may be determined according to ASTM D648-18 at 66 psi.

[0159] The polyolefin polymer may also have a specific elongation at break. For example, the elongation at break may be about 1,000% or less, for example, about 800% or less, for example, about 600% or less, for example, about 500% or less, for example, about 400% or less, for example, about 300% or less, for example, about 250% or less, for example, about 200% or less, for example, about 150% or less, for example, about 100% or less, for example, about 50% or less. The elongation at break may be about 0.5% or more, for example, about 1% or more, for example, about 2% or more, for example, about 5% or more, for example, about 10% or more, for example, about 25% or more, for example, about 50% or more, for example, about 100% or more, for example, about 250% or more, for example, about 500% or more, for example, about 750% or more. For example, the elongation at break may be relatively higher for polyolefin copolymers, such as polyolefin copolymer elastomers, than for polyolefin homopolymers. The elongation at break may be determined according to ASTM D638-14.

[0160] It should further be understood that the polyolefin polymers disclosed herein can be synthesized using any technique generally known in the art. For example, the polymers can be synthesized using any known process utilizing catalysts, activators, and reagents as generally known in the art. In this regard, the method for making or polymerizing the polyolefin polymers is not limited by the present invention.

[0161] III.D. Polyethylene The rigid coextruded polymer film of the present invention may include one or more layers comprising polyethylene (PE) or a polyethylene interpolymer. Any polyethylene or its interpolymer suitable for rigid coextruded films may be used. For example, the PE polymer material may be MDPE, HDPE, LLDPE, LDPE, or a blend thereof.

[0162] In one embodiment, the polyethylene-containing layer may comprise about 10 to 100 wt. % of a preferred ethylene / α-olefin interpolymer, such as a polymer of ultra-low density polyethylene (ULDPE) (about 0.910 to 0.914 g / cm 3and a melt index of about 0.7 to 1.0 dg / min) or linear low density polyethylene (LLDPE) (about 0.917 to 0.925 g / cm 3 The composition may contain up to 90% by weight of ethylene / octene-1 copolymers having densities in the range of 0.7 to 1.0 dg / min. and melt indexes of about 0.7 to 1.0 dg / min.

[0163] In one embodiment, the polyethylene layer has a viscosity of about 0.911 to 0.913 g / cm 3 and a melt index of about 0.8 to 0.9 dg / min, and about 75 to 90 wt. % of an ethylene / octene-1 copolymer, which is an ultra-low density polyethylene (ULDPE) having a density in the range of about 0.918 to 0.922 g / cm 3 and 10 to 25 wt. % linear low density polyethylene (LLDPE) having a density in the range of about 0.8 to 0.9 dg / min. and a melt index of about 0.8 to 0.9 dg / min.

[0164] In another embodiment, the PE layer comprises an ethylene-α-olefin copolymer in an amount ranging from about 0 to about 15 parts by weight of the PE layer. The copolymer is an ultra-low density copolymer of ethylene and at least one C4 to C10 α-olefin produced by a polymerization process using a single-site polymerization catalyst, and has a density of about 0.859 to about 0.905 g / cm. 3 and a melt index in the range of about 0.4 to about 1.1 dg / min. The density may be expressed by any of the following numerical values: about 0.859, about 0.860, about 0.861, ..., about 0.903, about 0.904, and about 0.905 g / cm. 3 Similarly, the melt index can be defined by any number below, or as a range defined by any two numbers from about 0.4, about 0.45, about 0.5, ..., about 0.95, about 1.05, and about 1.1 dg / min, inclusive.

[0165] In another embodiment, the ethylene-α-olefin copolymer ranges from about 0 parts by weight to 15 parts by weight and can be produced in a polymerization process using either a single-site polymerization catalyst or a Ziegler-Natta polymerization catalyst, and the copolymer has a viscosity of about 0.909 to about 0.935 g / cm 3 and a melt index in the range of about 0.5 to about 1.5 dg / min. In other embodiments, the weight percent of the ethylene-α-olefin copolymer can be defined by any numeric value or as a range defined by any two numeric values ​​from about 0.0, 0.5, about 1.0, about 1.5, about 2.0, about 2.5, about 3.0, about 3.5, about 4.0, about 4.5, about 5.0, about 5.5, about 6.0, about 6.5, about 7.0, about 7.5, about 8.0, about 8.5, about 9.0, about 9.5, about 10.0, about 10.5, about 11.0, about 11.5, about 12.0, about 12.5, about 13.0, about 13.5, about 14.0, about 14.5, and about 15.0 parts by weight, inclusive of the endpoints of the range. The density may be expressed by any of the following numbers: about 0.909, about 0.910, about 0.911, ..., about 0.933, about 0.934, and about 0.935 g / cm 3 Similarly, the melt index range can be defined by any two numbers from about 0.5, about 0.55, about 0.60, ..., about 1.40, about 1.45, and about 1.50 dg / min, inclusive.

[0166] In another embodiment, ethylene and at least one C4-C 10 The aforementioned low density copolymers with α-olefins or ethylene and at least one C4-C 10 The at least one very low density copolymer with an α-olefin is selected from ethylene / butene-1 copolymers, ethylene / hexene-1 copolymers, ethylene / octene-1 copolymers, ethylene / octene-1 / butene-1 terpolymers and ethylene / hexene-1 / butene-1 terpolymers.

[0167] In one embodiment, the polyethylene has a viscosity of about 0.910 to 0.920 g / cm 3 and a melt index of about 0.8 to 1.2 dg / min.; and a linear low density polyethylene (LLDPE) of 0 to 100 wt. %, or preferably about 30 to 70 wt. %, or more preferably 30 to 50 wt. %, ethylene / octene-1 copolymer having a density of about 0.918 to 0.930 g / cm. 3 and a melt index of about 0.8-1.2 dg / min, or preferably 70-30 wt %, or more preferably 50-70 wt %, of said copolymers.

[0168] C4~C 10 α-olefins also include cyclic counterparts.

[0169] III.E. Hydrocarbon Resins The polymeric film structure as disclosed herein comprises a two-layer PP stack, one of the layers of which is a barrier layer that is not primarily polypropylene but is primarily comprised of polypropylene and a hydrocarbon resin.

[0170] Generally, these hydrocarbon resins include resins made from petroleum-based feedstocks. For example, these resins can be synthesized from fractional distillation by-products of petroleum cracking. In particular, these hydrocarbon resins can include resins produced by hydrogenation of resinous polymerization products obtained by polymerization of mixed unsaturated monomers derived from deep petroleum cracking, as well as higher polymers obtained by polymerization and / or copolymerization of terpene hydrocarbons, which can then be hydrogenated under pressure.

[0171] The hydrocarbon resin may include, but is not limited to, an aliphatic hydrocarbon resin, an aromatic hydrocarbon resin, an aliphatic / aromatic hydrocarbon resin, or a mixture thereof. For example, the aliphatic / aromatic hydrocarbon resin may be a partially hydrogenated aromatic hydrocarbon resin. Furthermore, for the aliphatic hydrocarbon resins, they may be cycloaliphatic hydrocarbon resins. In addition to or instead of the above, the hydrocarbon resin may be a polyterpene resin, a terpene phenolic resin, a rosin ester, a rosin acid, a grafted resin, and a mixture thereof.

[0172] In one embodiment, the hydrocarbon resin can comprise an aliphatic, such as an at least partially hydrogenated aliphatic hydrocarbon resin. In another embodiment, the hydrocarbon resin can comprise an aliphatic / aromatic hydrocarbon resin, such as an at least partially hydrogenated aliphatic-aromatic hydrocarbon resin. In a further embodiment, the hydrocarbon resin can comprise an aromatic resin, such as an at least partially hydrogenated aromatic hydrocarbon resin. In another further embodiment, the hydrocarbon resin can comprise an alicyclic hydrocarbon resin, such as an at least partially hydrogenated cycloaliphatic resin. In another embodiment, the hydrocarbon resin can comprise an alicyclic / aromatic hydrocarbon resin, such as an at least partially hydrogenated alicyclic / aromatic hydrocarbon resin. In another further embodiment, the hydrocarbon resin can comprise a polyterpene resin, a terpene phenolic resin, a rosin ester, a rosin acid, a grafted resin, or a mixture thereof.

[0173] In one embodiment, the hydrocarbon resin can be an aromatic resin or a non-aromatic resin. In one embodiment, the hydrocarbon resin can be an aromatic resin. In another embodiment, the hydrocarbon resin can be a non-aromatic resin. For example, the hydrocarbon resin can be an aliphatic resin or an aliphatic / aromatic resin. In either case, the hydrocarbon resin can have an aromatic content of 0% by weight or greater, such as about 1% by weight or greater, such as about 2% by weight or greater, such as about 5% by weight or greater, 10% by weight or greater, such as about 15% by weight or greater. The aromatic content can be less than 100% by weight, such as about 90% by weight or less, such as about 70% by weight or less, such as about 60% by weight or less, such as about 50% by weight or less, such as about 40% by weight or less, such as about 20% by weight or less, such as about 15% by weight or less, such as about 10% by weight or less, such as about 5% by weight or less, such as about 2% by weight or less, such as about 1% by weight or less, or such as about 0.5% by weight or less. In one embodiment, the hydrocarbon resin can have an aromatic content of 0% by weight.

[0174] Generally, hydrocarbon resins may include hydrocarbon resins produced by the polymerization of various monomers. For example, these may include dienes (e.g., linear dienes), aromatic monomers, and natural monomers. Generally, some of these monomers may be derived from naphtha. Diene monomers may include piperylene, such as 1,3-pentadiene, 2-methyl-2-butene, etc. Diene monomers may also include cyclopentadiene and dicyclopentadiene. In addition, aromatic monomers may include, but are not limited to, styrene (including its derivatives), indene (including its derivatives), and others from C9-aromatic naphtha streams. As an example, styrene aromatics may include styrene, derivatives of styrene, and substituted styrenes. Specific examples of aromatics may include styrene, alpha-methylstyrene, beta-methylstyrene, indene, methylindene, and vinyltoluene. Natural monomers may also include natural monomers such as terpenes, such as alpha-pinene or beta-carene. Furthermore, it should be understood that these monomers may be used alone or in combination. In particular, one or more aromatic monomers and / or one or more natural monomers may be used in combination with the diene.

[0175] The hydrocarbon resins can be polymerized using any technique commonly known in the art. For example, a catalyst is commonly used in the polymerization. Examples of catalysts include AlC l3 and BF3. The polymerization may also utilize other modifiers or reagents. For example, the polymerization may utilize weight control modifiers to control the molecular weight distribution of the hydrocarbon resin. These may include, but are not limited to, monoolefin modifiers such as 2-methyl, 2-butene. They may also be used to control the MWD of the final resin.

[0176] Specific examples of commercially available hydrocarbon resins include rosin and rosin esters, phenol-modified styrene and methylstyrene resins, styrenated terpene resins, terpene-aromatic resins, terpene-phenolic resins, aliphatic-aromatic resins, cycloaliphatic / aromatic resins, C5 aliphatic resins, C9 aliphatic resins, C9 aromatic resins, C9 aliphatic / aromatic resins, and acid-modified C5 resins, C5 / C9 resins, and acid-modified C5 / C9 resins, mixed aromatic / cycloaliphatic resins, hydrogenated terpene aromatic resins, and mixtures thereof. In a particular embodiment, the hydrocarbon resin can include a C9 resin, such as an aromatic C9 resin.

[0177] Additionally, it should be understood that some of these resins may be polymerized. For example, a C5 monomer-based resin may be the polymerization product of at least C5 monomers. Similarly, a C9 monomer-based resin may be the polymerization product of at least C9 monomers. C5 monomers may include, for example, 1-pentene, isoprene, cyclopentadiene, 1,3-pentadiene, or mixtures thereof. C9 monomers may include, for example, indene, vinyl-toluene, alpha-methylstyrene, beta-methylstyrene, or mixtures thereof.

[0178] The hydrocarbon resin may also be hydrogenated. For example, the hydrocarbon resin may be partially, substantially, or fully hydrogenated. For example, in one embodiment, the hydrocarbon resin may be at least partially hydrogenated. In another embodiment, the hydrocarbon resin may be substantially hydrogenated. In a further embodiment, the hydrocarbon may be fully hydrogenated. In this regard, as used herein, "at least partially hydrogenated" means that the resin may contain less than 90% olefinic protons, such as less than 80% olefinic protons, for example less than 70% olefinic protons, for example less than 60% olefinic protons, for example less than 50% olefinic protons, for example less than 40% olefinic protons, for example less than 30% olefinic protons, for example less than 25% olefinic protons, and may contain 5% or more olefinic protons, such as 10% or more olefinic protons, for example 15% or more olefinic protons, for example 20% or more olefinic protons, for example 25% or more olefinic protons, for example 30% or more olefinic protons. Additionally, as used herein, "substantially hydrogenated" means that the resin may contain less than 5% olefinic protons, such as less than 4% olefinic protons, such as less than 3% olefinic protons, such as less than 2% olefinic protons, and may contain 0.1% or more olefinic protons, such as 0.5% or more olefinic protons, such as 0.8% or more olefinic protons, such as 1% or more olefinic protons, such as 1.5% or more olefinic protons, such as 2% or more olefinic protons.

[0179] With respect to hydrogenation, the degree of hydrogenation can be 50% or more, for example 60% or more, for example 70% or more, for example 80% or more, for example 85% or more, for example 90% or more, for example 95% or more, for example 96% or more, for example 97% or more, for example 98% or more, for example 99% or more, for example 100%. The degree of hydrogenation can be 100% or less, for example 99% or less, for example 98% or less, for example 95% or less, for example 90% or less, for example 85% or less, for example 80% or less, for example 75% or less. Without intending to be limited by theory, the degree of hydrogenation can affect the barrier properties. For example, a higher degree of hydrogenation can improve the barrier properties of the material and the resulting layer / film.

[0180] In one embodiment, the hydrocarbon resin may comprise one or more oligomers. For example, such oligomers may include dimers, trimers, tetramers, pentamers, and / or hexamers. The oligomers may be derived from petroleum distillates boiling in the range of 30°C to 210°C and / or may be by-products of resin polymerization. The oligomers may have a number average molecular weight of about 100 g / mol or more, such as about 115 g / mol or more, for example, about 130 g / mol or more, such as about 150 g / mol or more, for example, about 175 g / mol or more, for example, about 200 g / mol or more to about 500 g / mol or less, for example, about 450 g / mol or less, such as about 400 g / mol or less, for example, about 350 g / mol or less, for example, about 300 g / mol or less, such as about 270 g / mol or less, for example, about 250 g / mol or less, for example, about 225 g / mol or less. Molecular weight can be determined using techniques known in the art, such as gel permeation chromatography.

[0181] These oligomers include oligomers of cyclopentadiene, oligomers of substituted cyclopentadiene, oligomers of cyclopentadiene and substituted cyclopentadiene, oligomers of C4-C6 conjugated diolefins, oligomers of C8-C 10These may include, but are not limited to, oligomers of aromatic olefins, and combinations thereof. Additionally, other monomers may also be present, including C4-C6 mono-olefins, terpenes, and / or aromatic monomers. Furthermore, as noted above, it should be understood that such oligomers may be at least partially hydrogenated or substantially hydrogenated.

[0182] In a particular embodiment, the hydrocarbon resin can be derived from cyclopentadiene. In this regard, the hydrocarbon resin can be a polycyclopentadiene. For example, the hydrocarbon resin can be produced by polymerization (e.g., thermal polymerization) of cyclopentadiene. For example, the polymerization can be of cyclopentadiene (e.g., unsubstituted cyclopentadiene), substituted cyclopentadiene, dicyclopentadiene, methylcyclopentadiene, or mixtures thereof. Such resins can also further comprise aliphatic or aromatic monomers as described herein. Such cyclopentadiene can be present in the hydrocarbon resin in an amount of 50% by weight or more of the hydrocarbon resin, such as about 60% by weight or more, such as about 70% by weight or more, such as about 80% by weight or more, such as about 85% by weight or more, such as about 90% by weight or more, for example about 93% by weight or more. Cyclopentadiene may constitute less than 100% by weight of the hydrocarbon resin, such as about 99.5% by weight or less, such as about 99% by weight or less, such as about 98% by weight or less, such as about 97% by weight or less, such as about 95% by weight or less, for example about 90% by weight or less.

[0183] In one particular embodiment, dicyclopentadiene may constitute a majority of the cyclopentadiene utilized in forming the hydrocarbon resin. In this regard, dicyclopentadiene may constitute at least 50% by weight, e.g., at least 60% by weight, e.g., at least 70% by weight, e.g., at least 80% by weight, e.g., at least 85% by weight, e.g., at least 90% by weight to 100% by weight or less, e.g., about 99% by weight or less, e.g., about 97% by weight or less, e.g., about 95% by weight or less, e.g., about 90% by weight or less, of the cyclopentadiene utilized in the hydrocarbon resin. Furthermore, the foregoing weight percentages may also apply to the total amount of dicyclopentadiene present in the hydrocarbon resin.

[0184] As described herein, the hydrocarbon resin may include styrene. In this regard, the styrenic monomer may be utilized in the hydrocarbon resin in an amount of at least 1 wt%, such as at least 5 wt%, for example at least 10 wt% to 30 wt% or less, such as 20 wt% or less, for example 15 wt% or less, for example 10 wt% or less, for example 5 wt% or less. In one embodiment, the hydrocarbon resin may be substantially free of styrenic monomer. For example, the styrenic monomer may be present in an amount less than 1 wt%, for example less than 0.5 wt%, for example less than 0.1 wt%, for example 0 wt%.

[0185] As also provided herein, the hydrocarbon resin may include indene. In this regard, the indene-based monomer may be utilized in the hydrocarbon resin in an amount of at least 1 wt%, such as at least 5 wt%, for example at least 10 wt% to 30 wt% or less, such as 20 wt% or less, for example 15 wt% or less, for example 10 wt% or less, for example 5 wt% or less. In one embodiment, the hydrocarbon resin may be substantially free of indene-based monomer. For example, the indene-based monomer may be present in an amount less than 1 wt%, for example less than 0.5 wt%, for example less than 0.1 wt%, for example 0 wt%.

[0186] The hydrocarbon resin may have a particular viscosity determined in accordance with ASTM D3236-15 using a Brookfield viscometer and a size 21 spindle at a temperature of 160° C. The viscosity may be about 500 centipoise or more, such as about 700 centipoise or more, for example about 1,000 centipoise or more, such as about 1,500 centipoise or more, for example about 2,000 centipoise or more, such as about 3,000 centipoise or more, for example about 5,000 centipoise or more, such as about 8,000 centipoise or more, for example about 10,000 centipoise or more, such as about 13,000 centipoise or more, for example about 15,000 centipoise or more, such as about 18,000 centipoise or more, for example about 20,000 centipoise or more. The viscosity may be about 100,000 centipoise or less, such as about 80,000 centipoise or less, for example about 60,000 centipoise or less, for example about 50,000 centipoise or less, such as about 30,000 centipoise or less, for example about 25,000 centipoise or less, such as about 20,000 centipoise or less, for example about 17,000 centipoise or less, such as about 15,000 centipoise or less, for example about 12,000 centipoise or less, such as about 10,000 centipoise or less, for example about 7,000 centipoise or less, for example about 5,000 centipoise or less, 000 centipoise or less, such as about 4,000 centipoise or less, for example about 3,000 centipoise or less, for example about 2,000 centipoise or less, for example about 1,500 centipoise or less, such as about 1,000 centipoise or less, for example about 900 centipoise or less, for example about 800 centipoise or less, such as about 750 centipoise or less, for example about 700 centipoise or less, such as about 650 centipoise or less, for example about 625 centipoise or less, for example about 600 centipoise or less, such as about 550 centipoise or less.

[0187] The hydrocarbon resin may also have a specific molecular weight. For example, the hydrocarbon resin may have a weight average molecular weight of about 200 g / mol or more, for example, about 300 g / mol or more, for example, about 400 g / mol or more, for example, about 500 g / mol or more, for example, about 600 g / mol or more, for example, about 700 g / mol or more, for example, about 800 g / mol or more, for example, about 1,000 g / mol or more, for example, about 1,200 g / mol or more, for example, about 1,300 g / mol or more, for example, about 1,500 g / mol or more, for example, about 1,700 g / mol or more. The weight average molecular weight may be about 5,000 g / mol or less, for example, about 4,000 g / mol or less, for example, about 3,000 g / mol or less, for example, about 2,500 g / mol or less, for example, about 2,300 g / mol or less, for example, about 2,000 g / mol or less, for example, about 1,800 g / mol or less, for example, about 1,600 g / mol or less, for example, about 1,500 g / mol or less, for example, about 1,400 g / mol or less, for example, about 1,200 g / mol or less, for example, about 1,000 g / mol or less, for example, about 800 g / mol or less, for example, about 700 g / mol or less, for example, about 600 g / mol or less. Molecular weight may be determined using techniques known in the art, such as gel permeation chromatography.

[0188] Similarly, the hydrocarbon resin may have a number average molecular weight of about 200 g / mol or more, such as about 300 g / mol or more, for example about 400 g / mol or more, for example about 500 g / mol or more, such as about 600 g / mol or more, for example about 700 g / mol or more, such as about 800 g / mol or more, for example about 1,000 g / mol or more, such as about 1,200 g / mol or more, for example about 1,300 g / mol or more, such as about 1,500 g / mol or more, for example about 1,700 g / mol or more. The number average molecular weight may be about 5,000 g / mol or less, such as about 4,000 g / mol or less, for example about 3,000 g / mol or less, such as about 2,500 g / mol or less, for example about 2,300 g / mol or less, such as about 2,000 g / mol or less, for example about 1,800 g / mol or less, such as about 1,600 g / mol or less, for example about 1,500 g / mol or less, such as about 1,400 g / mol or less, for example about 1,200 g / mol or less, such as about 1,000 g / mol or less, for example about 800 g / mol or less, such as about 700 g / mol or less, for example about 600 g / mol or less. In this regard, the hydrocarbon resin may have a polydispersity index of about 1 or more, such as about 1.2 or more, for example, about 1.5 or more, such as about 1.6 or more, for example, about 1.7 or more, such as about 1.8 or more, for example, about 1.9 or more, such as about 2 or more, for example, about 2.3 or more, such as about 2.5 or more to about 20 or less, such as about 10 or less, for example, about 8 or less, such as about 5 or less, for example, about 4.5 or less, such as about 4 or less, for example, about 3.5 or less, for example, about 3 or less. Molecular weight may be determined using techniques known in the art, such as gel permeation chromatography.

[0189] In this regard, in one embodiment, the hydrocarbon resin may be considered a low molecular weight hydrocarbon resin. In one particular embodiment, the hydrocarbon resin may be considered a high molecular weight hydrocarbon resin.

[0190] In addition, the hydrocarbon resin may have a specific glass transition temperature. For example, the glass transition temperature may be about 0°C or higher, for example, about 20°C or higher, for example, about 30°C or higher, for example, about 40°C or higher, for example, about 50°C or higher, for example, about 60°C or higher, for example, about 70°C or higher, for example, about 80°C or higher, for example, about 100°C or higher. The glass transition temperature may be about 250°C or lower, for example, about 200°C or lower, for example, about 180°C or lower, for example, about 160°C or lower, for example, about 150°C or lower, for example, about 130°C or lower, for example, about 100°C or lower, for example, about 90°C or lower, for example, about 80°C or lower, for example, about 60°C or lower. The glass transition temperature may be determined using techniques known in the art, such as differential scanning calorimetry.

[0191] Further, the hydrocarbon resin may have a specific flash point. For example, the flash point temperature may be about 100°C or higher, such as about 125°C or higher, for example, about 150°C or higher, for example, about 175°C or higher, for example, about 190°C or higher, for example, about 200°C or higher, for example, about 210°C or higher, for example, about 215°C or higher, for example, about 220°C or higher, for example, about 230°C or higher. The flash point temperature may be about 400°C or lower, for example, about 350°C or lower, for example, about 300°C or lower, for example, about 280°C or lower, for example, about 260°C or lower, for example, about 250°C or lower, for example, about 240°C or lower, for example, about 230°C or lower. The flash point temperature may be determined using techniques known in the art, such as in accordance with ASTM D92-90.

[0192] The hydrocarbon resin may also have a specified Ring and Ball softening point determined in accordance with ASTM E-28 (Revision 1996) at a heating and cooling rate of 10°C / min. For example, the softening point may be about 0°C or higher, such as about 20°C or higher, for example, about 40°C or higher, such as about 50°C or higher, for example, about 60°C or higher, such as about 80°C or higher, for example, about 100°C or higher, such as about 110°C or higher, for example, about 115°C or higher, such as about 120°C or higher, for example, about 125°C or higher. The softening point may be about 250°C or lower, such as about 225°C or lower, for example, about 200°C or lower, for example, about 180°C or lower, such as about 160°C or lower, for example, about 150°C or lower, for example, about 140°C or lower, such as about 130°C or lower, for example, about 125°C or lower, for example, about 120°C or lower.

[0193] In addition, hydrocarbon resins may also have a specific aniline point, which is generally the lowest temperature at which equal volumes of aniline and resin are miscible. Without intending to be limited by theory, the aniline point may provide an indication of the aromatic hydrocarbon content of the resin. For example, the aniline point may be about 0°C or higher, such as about 20°C or higher, for example, about 40°C or higher, for example, about 50°C or higher, for example, about 60°C or higher, for example, about 80°C or higher, for example, about 100°C or higher, for example, about 107°C or higher, for example, about 110°C or higher, for example, about 115°C or higher, for example, about 120°C or higher, for example, about 125°C or higher. The aniline point may be about 250°C or lower, for example, about 225°C or lower, for example, about 200°C or lower, for example, about 180°C or lower, for example, about 160°C or lower, for example, about 150°C or lower, for example, about 140°C or lower, for example, about 130°C or lower, for example, about 125°C or lower, for example, about 120°C or lower. Generally, equal volumes of aniline and resin are continuously stirred and heated until the two dissolve to form a homogeneous solution, then heating is stopped and the temperature at which both phases separate is recorded as the aniline point, which can be determined according to ASTM D611-12.

[0194] III.F. Ethylene-Vinyl Alcohol Copolymer Barrier Layer The rigid coextruded polymer films of the present invention may include one or more layers comprising EVOH that also function as a barrier layer.

[0195] The mole percent ethylene in the ethylene-vinyl alcohol copolymer, or EVOH copolymer, ranges from about 20 to about 55%. Lower ethylene content in the EVOH polymer corresponds to improved barrier properties. Stated another way, the mole percent ethylene in the EVOH copolymer is a number selected from the following set of numbers: 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, and 55.

[0196] In one embodiment, the mole percent ethylene in the EVOH layer is a number within the range defined by any two of the above numbers, inclusive of the endpoints.

[0197] EVOH can include saponified or hydrolyzed ethylene-vinyl acetate copolymers, such as those having a degree of hydrolysis of at least 50%. Stated another way, the degree of hydrolysis, in percent, is any one of the following values: 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, and 100.

[0198] It is also contemplated that two or more different EVOH copolymers as described herein may be used in the EVOH layer.

[0199] Preferably, the EVOH layer has a thickness in the range of 0.8 to 50 microns.

[0200] III.G. Polyamide and Polyester Barrier Layers The additional layer may also advantageously comprise a polymeric material selected from the group of polymers having the general names polyamide or nylon, such as PA6 and PA66. These polymeric films also include biaxially oriented polyamides.

[0201] Polyester barrier layers may also be included in the rigid films of the present invention. Examples of polyesters include PET, PBT, 3GT, etc. These polymer films also include biaxially oriented polyesters.

[0202] The polyamides and polyesters can be uniaxially or biaxially oriented polymers.

[0203] III.H. Optional Additives The PP stack layer or barrier layer or other layers in the polymer film structure may contain any additional additives as commonly utilized in the art, and further, the additional layers as defined herein may also contain such additives.

[0204] These additives may include, but are not limited to, nucleating agents, clarifying agents, slip additives, antiblocking additives (e.g., silica), color pigments, UV stabilizers, antioxidants, light stabilizers, flame retardants, antistatic agents, biocides, viscosity breakers, impact modifiers, plasticizers, fillers, reinforcing agents, lubricants, mold release agents, blowing agents, pearlizing agents, and the like.

[0205] In one embodiment, a nucleating agent may be utilized. Generally, the nucleating agent may have a molecular weight of about 1,000 g / mol or less, such as about 800 g / mol or less, such as about 500 g / mol or less, such as about 300 g / mol or less, such as about 200 g / mol or less. Generally, the nucleating agent may be utilized to reduce the crystallization time of the thermoplastic material.

[0206] Nucleating agents may include, but are not limited to, sodium benzoate, talc, glycerol alkoxide salts, cyclic carboxylates, bicyclic carboxylates, glycerolates, phosphines, phosphates, hexahydrophthalates, sugar alcohols, and the like.

[0207] For example, sugar alcohols may include mannitol or mannitol-based compounds, sorbitol or sorbitol-based compounds, nonitol or nonitol-based compounds such as 1,2,3-trideoxy-4,6:5,7-bis-0-((4-propylphenyl)methylene)nonitol, and the like.

[0208] For example, the phosphine can include a salt such as the sodium salt of 2,4,8,10-tetra(tert-butyl)-6-hydroxy-12H-dibenzo[d,g][1,3,2]dioxaphosphocin 6-oxide.

[0209] The phosphate can include hydroxy-bis[2,2'-methylenebis[4,6-di(tert-butyl)phenyl]phosphate, 2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphate, a salt thereof, or a mixture thereof. For example, the salt can be an aluminum salt, a lithium salt, a sodium salt, or a mixture thereof.

[0210] Other nucleating agents may include, but are not limited to, diols (e.g., (1R)-1-[(4R,4aR,8aS)-2,6-bis(3,4-dimethylphenyl)-4,4a,8,8a-tetrahydro-[1,-3]dioxino[5,4-d][1,3]dioxin-4-yl]ethane-1,2-diol, 1-[8-propyl-2,6-bis(4-propylphenyl)-4,4a,8,8a-tetrahydro-[1,3]dioxino[5,4-d][1,3]dioxin-4-yl]ethane-1,2-diol, and the like).

[0211] Other nucleating agents include amides (e.g., N-[3,5-bis(2,2-dimethylpropanoylamino)phenyl]-2,2-dimethylpropanamide), salts such as the calcium salt of (1S,2R)-cyclohexane-1,2-dicarboxylate with zinc octadecenoate, and / or cis-endo-bicyclo[2,2,1]heptane-2,3-dicarboxylic acid disodium salt with 13-docosenamid, (Z)- and amorphous silicon dioxide.

[0212] In one particular embodiment, the nucleating agent can include at least one bicyclic carboxylate, such as bicycloheptanedicarboxylic acid, disodium salt, such as bicyclo[2.2.1]heptanedicarboxylate. For example, the nucleating agent can include a blend of bicyclo[2.2.1]heptanedicarboxylate, disodium salt, 13-docosenamide, and amorphous silicon dioxide.

[0213] In another embodiment, the nucleating agent may include cyclohexanedicarboxylic acid, a calcium salt, or a blend of cyclohexanedicarboxylic acid, a calcium salt, and zinc stearate.

[0214] In one embodiment, one of the layers may include a nucleating agent, a slip additive, an anti-blocking additive, or a mixture thereof. For example, in one embodiment, the additive may include at least a nucleating agent. In another embodiment, the additive may include at least a slip additive. In a further embodiment, the additive may include at least an anti-blocking additive. In another further embodiment, the additive may include a mixture of at least two of a nucleating agent, a slip additive, and an anti-blocking additive. In another embodiment, the additive may include a mixture of a nucleating agent, a slip additive, and an anti-blocking additive.

[0215] Individual layers and / or polymeric film substrates may contain such additives in an amount of about 20% by weight or less, for example, about 15% by weight or less, for example, about 10% by weight or less, for example, about 8% by weight or less, for example, about 5% by weight or less, for example, about 4% by weight or less, for example, about 3% by weight or less, for example, about 2% by weight or less, for example, about 1% by weight or less, for example, about 0.5% by weight or less, for example, about 0.3% by weight or less, for example, about 0.1% by weight or less, for example, 0% by weight. The additives may be provided in an amount of about 0.001% by weight or more, for example, about 0.005% by weight or more, for example, about 0.01% by weight or more, for example, about 0.05% by weight or more, for example, about 0.1% by weight or more, for example, about 0.5% by weight or more. In this regard, it should be understood that such additives may not be present within a layer in one embodiment.

[0216] Advantageously, the following additives are preferred:

[0217] The range of usable slip agents is about 200-2000 ppm or 0.5-2.5% by weight of the layer. A preferred slip agent is erucamide or other fatty acid amides, such as oleamide. Slip agents lower the coefficient of friction of the film, allowing it to slide easily over a variety of surfaces.

[0218] Any film antiblocking agent known to those skilled in the art can be added to the film layer in the range of about 1000-5000 ppm or 0.5-2.5% by weight of the layer. Typical antiblocking agents, such as diatomaceous earth, synthetic silica, or talc, can be added to the inner and outer sealant layers of the film. Antiblocking materials are particularly useful for reducing the coefficient of friction between the film and the metal surface over which the film is pulled during the bag-making process.

[0219] Any processing aid known to those skilled in the art, preferably but not limited to, a fluoroelastomeric polymer, may be added to the outer and inner sealing layers of the polymeric film substrate.

[0220] The present invention is also directed to flexible containers containing packaged materials, which can be made from the aforementioned multilayer films in an FFS process. The FFS process and modifications thereof are described in U.S. Patent Nos. 5,538,590, 9,327,856, and 9,440,757, which are incorporated herein by reference in their entireties.

[0221] Although melt index ranges are specified herein, it is understood that polymers having melt indices characteristic of film-grade polymers can be used. The multilayer films of the present invention have the ability to form lap seals as well as fin seals. They also substantially reduce curl in laminates.

[0222] IV. Polymer Film Structures—Barrier Film Embodiments Exemplary embodiments of the present invention are described below.

[0223] IV.A.1. Embodiment 1 This embodiment comprises a coextruded, bi-layered rigid film of AB construction. The first layer, A, comprises primarily conventional polypropylene. The second layer, B, comprises primarily Impede® polymer. The rigid film has a thickness, measured in inches, ranging from about X to about Y. The rigid film of this embodiment provides improved barrier properties and improved stiffness.

[0224] The weight contents of A and B are independently in the range of 10 / 90 to 90 / 10. In other words, the A content is in the range of about 10% to about 90% by weight of the hard film, and the B content is in the range of about 10% to about 90% by weight of the hard film. In other words, the weight contents of A and B in the hard film, in weight percent of the hard film of this embodiment of the present invention, are selected from the following values: 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, and 90.

[0225] The contents of A and B may also be within a range defined by any two numbers from the above list, including the endpoints of such range.

[0226] IV.A.2. Embodiment 2 This embodiment includes a coextruded three-layered rigid film with an A1-B-A2 structure. The first layer A1 primarily comprises conventional polypropylene. The second layer B comprises Impede® polymer. The third layer A2 primarily comprises conventional PP, which may be the same grade or a different grade than the conventional PP in the first layer A1.

[0227] The rigid film has a thickness, measured in inches, ranging from about X to about Y. The rigid film of this embodiment provides improved barrier properties and improved stiffness.

[0228] The A1-B-A2 weight contents independently range from 43 / 14 / 43 to 10 / 80 / 10. In one embodiment, the A1 content independently ranges from about 10% to about 76% by weight of the rigid film. Similarly, the A2 content independently ranges from about 10% to about 76% by weight of the rigid film. The B content independently ranges from about 14% to about 80% by weight of the rigid film. Stated differently, the weight contents of A1 and A2 in the rigid film, in weight percent of the rigid film of this embodiment of the present invention, are selected from the following values: 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, and 76.

[0229] The content of A1 and A2 may also be within a range defined by any two numbers from the above list, including the endpoints of such range.

[0230] Similarly, the weight content of B in the hard film is selected from the following values, in weight percent of the hard film of this embodiment of the present invention: 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, and 80.

[0231] The B content can also be within a range defined by any two numbers from the above list, including the endpoints of such range.

[0232] IV.A.3. Embodiment 3 This embodiment includes a coextruded six-layered rigid film with an A1-B-T1-C-T2-A2 structure that includes one two-layered PP stack. The first layer A1 primarily contains conventional polypropylene. The second layer B contains Impede® PP polymer. The third layer T1 is a tie layer. The fourth layer C primarily contains EVOH. The fifth layer T2 is a tie layer. The sixth layer A2 primarily contains conventional polypropylene, which may be the same grade as the conventional PP in the first layer A1 or a different grade.

[0233] The rigid film has a thickness, measured in inches, ranging from about X to about Y. The rigid film of this embodiment provides improved barrier properties and improved stiffness.

[0234] The A1-B weight contents are independently in the range of 10 / 90 to 90 / 10. In other words, the A1 content is in the range of about 10% to about 90% of the total weight of the two layers A1+B, and the B content is in the range of about 10% to about 90% of the total weight of the two layers A1+B. In other words, the A1 content and the B content as a percentage of their total weight are selected from the following values, in weight percent of their total weight: 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, and 90.

[0235] The contents of A1 and B may also be within a range defined by any two numbers from the above list, including the endpoints of such range.

[0236] IV.A.4. Embodiment 4 This embodiment includes a coextruded eight-layered rigid film with an A1-B1-T1-C-T2-B2-T3-D structure containing one two-layered PP stack. The first layer A1 primarily contains regular polypropylene. The second layer B1 contains Impede® PP polymer. The third layer T1 is a tie layer. The fourth layer C primarily contains EVOH. The fifth layer T2 is a tie layer. The sixth layer B2 primarily contains Impede® polypropylene, either the same grade or a different grade than the Impede® PP in the second layer B1. The seventh layer is a tie layer. The eighth layer is a sealant layer.

[0237] The rigid film has a thickness, measured in inches, ranging from about X to about Y. The rigid film of this embodiment provides improved barrier properties and improved stiffness.

[0238] The A1-B1 weight contents are independently in the range of 10 / 90 to 90 / 10. In other words, the A1 content is in the range of about 10% to about 90% of the total weight of the two layers A1+B1, and the B1 content is in the range of about 10% to about 90% of the total weight of the two layers A1+B1. In other words, the A1 content and B1 content as a percentage of the total weight are selected from the following values, in weight percent of their total weight: 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, and 90.

[0239] The content of A1 and B1 may also be within a range defined by any two numbers from the above list, including the endpoints of such range.

[0240] IV.A.5. Embodiment 5 This embodiment includes a coextruded four-layered rigid film with an A1-B1-B2-A2 structure that includes two two-layered PP stacks. The first layer A1 contains primarily regular polypropylene. The second layer B1 contains Impede® PP polymer. The third layer B2 contains Impede® PP polymer. The fourth layer A2 contains primarily regular PP.

[0241] The rigid film has a thickness, measured in inches, ranging from about X to about Y. The rigid film of this embodiment provides improved barrier properties and improved stiffness.

[0242] The weight contents of A and B are independently in the range of 10 / 90 to 90 / 10. In other words, the (A1+A2) content is in the range of about 10% to about 90% by weight of the hard film, and the (B1+B2) content is in the range of about 10% to about 90% by weight of the hard film. In other words, the weight contents of (A1+A2) and (B1+B2) in the hard film are selected from the following values, in weight percent of the hard film of this embodiment of the present invention: 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, and 90.

[0243] The contents of (A1+A2) and (B1+B2) are also within a range defined by any two numbers from the above list, including the endpoints of such range.

[0244] IV.A.6. Embodiment 6 This embodiment includes a coextruded seven-layered rigid film with an A1-B1-A2-T1-A3-B2-A4 structure that includes two three-layered PP stacks. The first layer A1 contains primarily conventional polypropylene. The second layer B1 contains Impede® PP polymer. The third layer B2 contains primarily conventional PP polymer. The fourth layer is a tie layer. The fifth layer A3 contains primarily conventional PP. The sixth layer B1 contains Impede® PP polymer. The seventh layer B2 contains primarily conventional PP polymer.

[0245] The rigid film has a thickness, measured in inches, ranging from about X to about Y. The rigid film of this embodiment provides improved barrier properties and improved stiffness.

[0246] The A and B weight contents are independently in the range of 10 / 90 to 90 / 10. In other words, the (A1+A2+A3+A4) content is in the range of about 10% to about 90% by weight of the combined A and B polymers, and the (B1+B2) content is in the range of about 10% to about 90% by weight of the combined A and B polymers. In other words, the weight contents of (A1+A2+A3+A4) and (B1+B2) in the total weight of the A and B polymers are selected from the following values, in weight percent of the total weight of the A and B polymers: 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, and 90.

[0247] The contents of (A1+A2+A3+A4) and (B1+B2) are also within the range defined by any two numbers from the above list (including the endpoints of such range).

[0248] IV.A.7. Additional Embodiments Additional embodiments include the coextruded rigid films illustratively set forth in Table 3 below, some of which are illustrated in Figure 1. The nomenclature for the coextruded films included in Table 3 is provided in Table 2.

[0249] [Table 3]

[0250] [Table 4]

[0251] One preferred method of producing the film is the so-called blown film process. After production, the film is cut longitudinally to the appropriate width. A preferred method of producing multilayer films is by using a blown film coextrusion process, although other methods of producing films may also be used.

[0252] V. Molded Articles from Polymeric Film Structures The polymer film structures of the present invention may form at least a portion of a molded polymer article. The polymer film structures and resulting molded polymer articles may be formed using various techniques known in the art. These techniques may include, but are not limited to, thermoforming, blow molding, injection molding, compression molding, rotational molding, and the like. For example, in one embodiment, the polymer film structures and resulting molded polymer articles may be formed by thermoforming to create a thermoformed molded polymer article. In another embodiment, the polymer film structures and resulting molded polymer articles may be formed by blow molding to create a blown molded molded polymer article. In a further embodiment, the polymer film structures and resulting molded polymer articles may be formed by injection molding to create an injection molded molded polymer article. In yet another embodiment, the polymer film structures and resulting molded polymer articles may be formed by compression molding to create a compression molded molded polymer article. However, it should be understood that other processing techniques may also be utilized in accordance with the present invention.

[0253] In one embodiment, the polymeric film structures and molded polymer articles as disclosed herein can be formed by exposing a barrier layer, such as a PP stack layer, and any additional layers as defined herein to a thermoforming process. Thermoforming generally involves heating the layers to a particular temperature, molding the layers in a mold, and then optionally trimming the molded polymer article to create the desired article.

[0254] The particular forming technique is not critical, and any of a variety of conventional processes can be used in the present invention. Suitable techniques can include, for example, vacuum forming, plug-assist forming, male mold forming, press molding, and the like. For example, the layer can be fed into a heating device (e.g., a convection oven, a resistance heater, an infrared heater, etc.) that heats the layer to a temperature sufficient to deform or stretch the polymer. This temperature generally can be above the glass transition temperature, but can be below the melting temperature. For example, the thermoforming temperature can be about 10°C or higher, e.g., about 20°C or higher, e.g., about 30°C or higher, e.g., about 40°C or higher, e.g., about 45°C to about 100°C or lower, e.g., about 80°C or lower, e.g., about 60°C or lower, below the melting temperature. For example, the layer can be heated to a temperature of about 30°C or higher, e.g., about 40°C or higher, e.g., about 50°C or higher, e.g., about 60°C to about 200°C or lower, e.g., about 150°C or lower, e.g., about 130°C or lower, e.g., about 120°C or lower, e.g., about 110°C or lower. Once heated, the layer can then be fed into a mold where a force (e.g., suction) is applied to the layer to cause it to conform to the contours of the mold. The mold cavity imparts the shape of the article to the layer while simultaneously allowing the material to cool significantly below its melting point so that it solidifies sufficiently to retain its shape when removed from the mold.

[0255] In one embodiment, a thermoforming process may be utilized. The film layer is fed into a heating device, which heats the layer to a temperature sufficient to deform the layer. As described above, any of a variety of heating devices may be used in the thermoforming process. Once heated, the layer is fed into a molding device, where it is formed into an article. As described above, any of a variety of molding devices may be used in the thermoforming process. The layer then conforms to the contours of a mold, resulting in a polymeric film structure and a molded polymeric article. Multiple layers, including a layer that is just a PP stack as a barrier layer as disclosed herein, or a single layer may be used. In addition, thermoforming applications may also include forming, filling, and sealing applications as commonly known in the art.

[0256] In another embodiment, the molded polymeric article may be a blow-molded molded polymeric article. Blow-molded articles may be formed using extrusion blow molding, injection blow molding, or injection stretch blow molding techniques. Regardless of the method, blow molding generally involves providing a polymeric material into a hollow mold cavity, blowing air into the material to shape it within the mold, and then optionally trimming the molded polymeric article to create the desired article. For example, a polymeric material containing the aforementioned components of the barrier layer (i.e., polyolefin polymer, hydrocarbon resin, and optional additives) may be provided directly into the hollow mold cavity. Once inserted, the mold is closed and the parison is held in place. A nozzle or pin may then be inserted into the open end of the parison to introduce air and expand the parison to the shape of the mold. The mold temperature may be about 0°C or higher, such as about 5°C or higher, such as about 10°C or higher, such as about 20°C or higher, such as about 30°C or higher, such as about 40°C or higher, or such as about 45°C or higher, above the melting temperature of the material. The mold temperature can be about 90°C or lower, e.g., about 85°C or lower, e.g., about 80°C or lower, below the melting temperature of the material. In one embodiment, the mold temperature can be from above 0°C to the crystallization temperature of the material. In certain embodiments, for example, the layer can be heated in the mold to a temperature of about 30°C to about 150°C, in some embodiments about 50°C to about 130°C, and in some embodiments, about 60°C to about 120°C, until the layer is formed. The mold cavity imparts the shape of the article to the layer while simultaneously cooling the material to a temperature significantly below its melting point so that the material solidifies sufficiently to retain its shape upon removal from the mold. Additionally, cold air can be introduced into the mold to solidify the polymer. Once the layer is formed, the mold is opened and the molded polymeric article is removed. Optionally, the molded polymeric article is then trimmed as needed to produce the desired article. One example of a blow molding process, particularly an injection stretch blow molding process, is for forming a bottle.

[0257] Another processing technique that may be utilized in accordance with the present invention is injection molding. Generally, forming an injection molded article involves plasticizing or heating a polymeric material, injecting the material into a mold, filling the mold with the polymeric material, cooling the article, and demolding / ejecting the article.

[0258] Depending on the processing technique utilized, the polymeric film structures and molded polymeric articles can be monolayer or multilayer. In one embodiment, the polymeric film structures and molded polymeric articles can be monolayer. In another embodiment, the polymeric film structures and molded polymeric articles can be multilayer. For example, multilayer films and articles can be formed using thermoforming. Alternatively, monolayer films and articles can be formed using thermoforming, blow molding, or injection molding. Furthermore, using the above processing techniques, in some embodiments, the polymeric films and articles as disclosed herein can be non-oriented.

[0259] Furthermore, by utilizing the polyolefin polymers and hydrocarbon resins disclosed herein, the resulting substrate and barrier layer and / or polymeric material can experience minimal mold shrinkage. For example, mold shrinkage can be 10% or less, such as 8% or less, such as 6% or less, such as 5% or less, such as 4% or less, such as 3% or less, such as 2.5% or less, such as 2% or less, such as 1.8% or less, such as 1.6% or less, such as 1.5% or less, such as 1.4% or less, such as 1.3% or less, such as 1.2% or less, such as 1.1% or less, or such as 1% or less. Mold shrinkage can be 0.01% or more, such as 0.05% or more, such as 0.1% or more, such as 0.3% or more, such as 0.5% or more, such as 0.8% or more, such as 1% or more, such as 1.1% or more, such as 1.3% or more, or such as 1.5% or more. Such mold shrinkage can be in the flow direction in one embodiment. In another embodiment, such mold shrinkage can be in the cross-flow direction. In further embodiments, such mold shrinkage can be in the flow direction and the cross-flow direction.

[0260] The mold shrinkage and mechanical properties as disclosed herein may allow polymeric film structures and barrier layers to mimic the performance and attributes of other polymers (such as polystyrene), thereby enabling these materials to be used in a wide variety of applications, some of which are provided herein. In particular, the materials disclosed herein may generally exhibit flexural modulus and other mechanical properties that mimic those of other polymers, particularly polystyrene.

[0261] As described above, the molded polymeric article may have an average final wall thickness of more than 200 μm, for example, 210 μm or more, for example, 220 μm or more, for example, 240 μm or more, for example, 250 μm or more, for example, 300 μm or more, for example, 500 μm or more, for example, 700 μm or more, for example, 900 μm or more, for example, 1 mm or more, for example, 3 mm or more, for example, 5 mm or more. The molded polymeric article may have an average final wall thickness of 1.25 cm or less, for example, 1 cm or less, for example, 8 mm or less, for example, 5 mm or less, for example, 3 mm or less, for example, 2 mm or less, for example, 1 mm or less, for example, 800 μm or less, for example, 500 μm or less, for example, 400 μm or less, for example, 350 μm or less, for example, 300 μm or less, for example, 280 μm or less, for example, 270 μm or less. Such an average thickness may be obtained by averaging the wall thicknesses of the molded polymeric article.

[0262] Regardless of the technique utilized, the polymeric film structures including the barrier layer can be molded or utilized for a wide variety of different three-dimensional articles. For example, the resulting articles can be packaging products for the food, medical, or general retail industries, such as packages, cups, tubs, buckets, jars, boxes, containers, lids, trays (e.g., for food), blisters, clamshells, bottles, pouches, appliance parts (e.g., refrigerator liners), pallets, automotive or aircraft parts, such as dash panels, door panels, utility vehicle beds, and others. In a particular embodiment, the molded polymeric article can be a packaging article, such as a food packaging article. In particular, because of the materials utilized in the polymeric film structures and barrier layers, the film structures and layers can also meet U.S. Food and Drug Administration guidelines and compliance, particularly for use as food packaging articles.

[0263] Furthermore, even with materials utilized with polyolefin polymers such as those disclosed herein, the barrier layer and resulting polymer film structure may also be recyclable. For example, if the polyolefin polymer is polypropylene, utilization of certain materials such as those disclosed herein may still allow the barrier layer and resulting polymer film structure to be coded as Class 5 materials for recycling purposes.

[0264] Having generally discussed embodiments of the present disclosure, the present disclosure can be further understood by the following non-limiting examples. [Example]

[0265] experiment I. Test Method IA melt viscosity Melt viscosity is measured according to ASTM D 3236 (350°F) using a Brookfield Digital Viscometer (Model DY-III, version 3) and a disposable aluminum sample chamber. The spindle used is typically an SC-31 hot-melt spindle, suitable for measuring viscosities in the 10 to 100,000 centipoise range. The sample is poured into the chamber, which is then inserted into a Brookfield Thermosel and secured in place. The sample chamber has a notch in the bottom that fits the bottom of the Brookfield Thermosel to prevent the chamber from rotating when the spindle is inserted and rotating. The sample (approximately 8 to 10 g of resin) is heated to the required temperature until the molten sample is approximately 1 inch below the top of the sample chamber. The viscometer device is lowered, submerging the spindle into the sample chamber. The downward movement continues until the viscometer bracket is aligned with the Thermosel. Start the viscometer and set it to operate at a shear rate that results in a torque reading within 40-60 percent of the total torque capacity, based on the rpm output of the viscometer. Take readings every minute for approximately 15 minutes, or until the value stabilizes, at which point record the final reading.

[0266] IB Melt Index The melt index (I2, or MI) of ethylene-based polymers is measured according to ASTM D-1238, condition 190°C / 2.16 kg. For high I2 polymers, i.e., I2 of 200 g / mol or greater, the melt index is preferably calculated from the Brookfield viscosity, as described in U.S. Patent Nos. 6,335,410, 6,054,544, and 6,723,810. I2(190°F / 2.16 kg) = 3.6126 [10(log(η) - 6.6928) / - 1.1363] - 9.31851, where η = melt viscosity at 350°F (cP).

[0267] IC oxygen permeability The oxygen transmission rate (OTR) test determines the reduction in oxygen transmission in the rigid films used to prepare the rigid containers of the present invention.

[0268] OTR was determined according to ASTM D 3985 standard at 23°C and 80% relative humidity. Rigid film samples of appropriate size were cut on a cutting mat using a MOCON template for a Mocon Oxtran machine. The cut sample was then placed in the Mocon Oxtran and fixed in place according to the specific machine requirements. Parameter settings were based on industry standard testing. The sample was tested until the graph showed a plateau. The test time varied from 8 to 70 hours depending on the graph curve. All results are reported in cm 3 / 100in 2 Recorded in units of / day.

[0269] [Table 5]

[0270] Table 6 below provides OTR and water vapor transmission rate (WVTR or MVTR) data for control and experimental samples extruded, thermoformed, or prepared on an FFS machine.

[0271] [Table 6]

[0272] From the above data it is clear that the barrier enhancements compared to polystyrene and common polypropylene are as follows: 80% improvement in OTR compared to general polypropylene 90% OTR improvement compared to polystyrene 100% MVTR improvement compared to polystyrene 80% improvement in MVTR compared to general polypropylene

[0273] ID Differential Scanning Calorimetry Differential scanning calorimetry (DSC) measures the heat flow to or from a material as a function of time or temperature. It determines polymer crystallinity, the glass transition temperature of amorphous polymers, and the melting temperature of crystalline polymers based on the heat required to melt the polymer. DSC is used, for example, to measure crystallinity in polyethylene (PE) and polypropylene (PP) based samples.

[0274] Two samples were tested by DSC. The first sample was XPP resin in pellet form (the "XPP pellet" sample). The second sample consisted of a coextruded multilayer sheet (ABA) consisting of outer layers of polypropylene (PP) with an inner core layer of barrier-grade XPP polypropylene ("sheet") sample.

[0275] The samples were tested using a TA Instruments Q200 DSC machine. The test method followed ASTM D3418-15+ standard. A specimen weighing approximately 8 mg was sealed in an aluminum DSC sample pan for analysis. The specimen was first equilibrated at 25°C, then heated to 200°C and held isothermally for 5 minutes. The sample was then cooled to 25°C and held isothermally for 5 minutes. After the isothermal step, the sample was reheated to 200°C, with all heating ramps performed at a rate of 10°C / min, all under a nitrogen environment.

[0276] The glass transition temperature (Tg) was measured as the inflection point of the endothermic step transition. The endothermic transition was integrated to measure the peak melting transition temperature (Tm) and enthalpy heat of fusion (ΔHf). Two heating cycles were superimposed as shown in Figures 2 and 3. The as-received percent crystallinity was calculated using the enthalpy value from the transition in the first heating cycle and the literature value for the heat of fusion for 100% crystalline PP. A summary of the results is shown in Table 7.

[0277] Enthalpies were reported as percent crystallinity (%Cryst.) by normalizing the observed heat of fusion to that of a theoretical 100% crystalline sample. Literature values ​​were relative to 100% crystallinity. %Cryst. was calculated by dividing the heat of fusion (Hf) determined from the first heating curve by the theoretical heat of fusion of PP, 207 J / g, and multiplying this quantity by 100. %Cryst.=(Hf / 207J / g)×100

[0278] The XPP pellet sample exhibited a higher glass transition, a melting transition with only one peak, and a slightly higher as-received percent crystallinity. The melting peak for the XPP pellet sample was observed at about 163°C. See Figure 2.

[0279] On the other hand, the sheet sample showed a bimodal melting peak, i.e., a melting temperature at 163°C and a second low-temperature peak at 148°C, which is believed to be on the lower side of the PP melting temperature, see Figure 3.

[0280] [Table 7]

[0281] Isotactic polypropylene homopolymer has a high degree of crystallinity, ranging from 30 to 60%. Here, the XPP resin pellets were indeed homopolymer-based. However, the sheet samples were constructed as an ABA structure equivalent to:

[0282] Random copolymer PP / Homopolymer XPP / Random copolymer PP The XPP resin sample and the ABA sheet sample exhibited similar %Cryst., i.e., about 40% %Cryst. Surprisingly, the sheet sample exhibited a secondary low-temperature peak. Since the XPP raw material in pellets is made in small batches using PP monomer in powder form, the resulting low-temperature peak may be due to a bimodal melt transition, a blend of high and low molecular weight PP in either the reactor or extrusion stage, or low molecular weight ethylene, rubber, or a combination of both to make a random copolymer PP, or a commercially available bimodal material present in the skin layer of the ABA structure.

[0283] IE Score & Snap Test Score and snap tests were performed on three samples. 1. 0.040" thick PP / XPP / PP rigid sheet, 2. 0.020 inch thick PP / XPP / bonded / EVOH / bonded / PP plastic sheet; and 3. 0.040" thick PP / XPP / bonded / EVOH / bonded / PP plastic sheet.

[0284] A 10-inch long plastic sheet was used for the test. A narrow, shallow cut down to 0.0045 inches was made using a disposable plastic scoring knife. The plastic sheet was placed on a work bench with the cut facing up, over the edge of the work bench. The overhang was snapped with a quick but consistent moving impact. The cut acted as a guide for the break to propagate through the thickness of the sheet, separating the sheet into two pieces with straight, relatively clean edges. The end result was a cut in the sheet with a smooth, clean edge across its width.

[0285] In the table below, the following notation is used: PP 6025N PP homopolymer PP R01C-00 PP random copolymer Impede® MP 1250-TC Barrier Polypropylene PX 3838 Linear Low Density Polyethylene (LLDPE) BX6804B Ethylene-vinyl alcohol copolymer (EVOH)

[0286] [Table 8]

[0287] IF Polypropylene Single Serve Cup - Form Fill Seal Test Three samples were run through a Gabler M60 thermoforming machine to thermoform containers such as cups or capsules to replace PS in current single-serve coffee pods. Any barrier film that provides an OTR of less than 1 cc-mil / 100 in2-day is considered a high-to-medium barrier material. This example relates to thermoforming testing of PP / XPP / PP at 0.040 inches for single-serve coffee pods. (1) XPP 803 polypropylene is an experimental barrier PP sample. It contains an ABA structure, where A is a PP random copolymer and B is IMPEDE® MP 2250-XP1 polypropylene. (2) XPP 802 polypropylene is also an experimental barrier sample. It contains an ABA structure, where A is PP homopolymer and B is IMPEDE® MP 1250 polypropylene. (3) XPTPC polypropylene is the experimental barrier sample. It is a talc-filled homopolymer of PP with CPS 606 barrier additive in the core layer in four different gauges designed around creamer and pudding cups.

[0288] Overall, the test was successful in terms of processing and output. When compared across all variables, XPP 802 demonstrated advantages in terms of the FFS process, including properties such as shrinkage, ease of forming, and part trimming. Note that XPP 802 was fabricated at 0.040 inch, but not in the thin and thick gauge FFS applications of 0.020 inch or 0.045 inch, as were the other samples.

[0289] For the XPP 803 sample, the cup appeared good with a clean trim. Attempts to puncture the hot cup were unsuccessful, although PP single-serve capsules typically require a minimum 24-hour cooling / setting period. For the XPP 802 sample, the cup did not shrink in the mold. For the XPTPC sample, the cup appeared good, cloudy with inorganic filler, and had a clean trim. Attempts to puncture the hot cup were unsuccessful, although PP single-serve capsules typically require a minimum 24-hour cooling / setting period. These cups were the stiffest of the three samples tested.

[0290] In one experiment, XPP 802 is tested in thin and thick gauges on a fully functional FFS line for a 10-minute test under real-world conditions, including hydrogen peroxide sterilization, forming, filling, capping, and trimming of parts. Shrinkage in the longitudinal and transverse directions is evaluated to determine how the material and machine will respond.

[0291] II. Extrusion test ABA coextrusion tests were conducted at various gauges and widths to evaluate the performance of barrier-enhanced PP materials for conversion into containers on current production thermoforming and form-fill-seal equipment. Four grades were used in the tests. (1) XPP 801—Random copolymer base. This grade was used to evaluate its sheet extrusion performance as a polystyrene (PS) replacement for FFS application to determine scoring and snapping capabilities utilizing a standard pudding cup. (2) XPP 802—Homopolymer base. This grade was used to evaluate its sheet extrusion performance as a target barrier reinforcement and as a PS material replacement to evaluate performance utilizing an array tray tool. (3) XPP 803—Modified random copolymer base. This grade was used to evaluate its sheet extrusion performance and to form K-cups on a PS tool to evaluate moldability. Barrier performance testing was also performed on sheets formed with XPP 803. (4) PP 23H2A--random copolymer.

[0292] The tests were conducted on a production-scale coextruder for films with a 25 / 50 / 25 or 33 / 33 / 33 configuration. Standard extrusion parameters were used, but adapted for PP.

[0293] The gauge or thickness and width of the finished sheets were measured using a calibrated micrometer and measuring tape, along with online gauge measurements using a Mahlo gauging unit. Moisture content test results showed 0% moisture. Material shrinkage tests were performed on each formula at the beginning and end of the run. Finished sheets were tested 24 hours after production. The results are shown in Table 9 below. The final weight layer ratio was 25 / 50 / 25.

[0294] [Table 9]

[0295] III. Additional Examples III.A. Working Example As shown in Figure 4, a cup is made from the inventive rollstock or rigid sheet described in this disclosure. This rollstock offers enhanced barrier and stiffness over conventional PS and PP for thermoforming and form-fill-seal food and medical packaging. This rollstock is process compatible, including aseptic, hot-fill, retort, modified atmosphere packaging (MAP), HPP, FFS, and FS, for a variety of end uses. It provides controlled shrinkage and enhanced stiffness for a drop-in replacement of PS in thermoforming and FFS food packaging. In one embodiment, it also provides barrier improvements of up to 90% / 90% OTR / MVTR over conventional PP and up to 100% / 150% OTR / MVTR over conventional PS without the use of special barrier materials or coatings. Due to the enhanced stiffness, this material offers the potential for downgauging. In one embodiment, the rollstock comprises homopolymer PP, which includes at least one layer comprising at least one grade of Impede® resin. In one embodiment, the roll stock is extruded at a thickness ranging from 0.010 inches to 0.20 inches based on the customer's application. In one embodiment, the roll stock is white. In another embodiment, the roll stock is natural color. In one embodiment, the roll stock is made from XPP802 material grade.

[0296] III.B. Working Example As shown in Figure 5, a cup is made from the inventive rollstock or rigid sheet described in this disclosure. This rollstock provides enhanced barrier and stiffness over conventional PS and PP for thermoforming and form-fill-seal food and medical packaging. This rollstock is process compatible, including aseptic, hot-fill, retort, MAP, HPP, FFS, and FS, for a variety of end uses. In one embodiment, it provides controlled shrinkage and enhanced stiffness for a drop-in replacement of PS in thermoforming and FFS food packaging. In one embodiment, it also provides a barrier improvement of up to 90% / 90% OTR / MVTR over conventional PP and up to 100% / 150% OTR / MVTR over conventional PS, with an EVOH layer providing additional OTR barrier protection for shelf-stable food packaging. In one embodiment, the rollstock comprises homopolymer PP, which includes at least one layer comprising at least one grade of Impede® resin. In one embodiment, the rollstock is extruded at a thickness ranging from 0.010 inches to 0.20 inches based on the customer's application. In one embodiment, the PP layers include an Impede® layer (total weight % of PP is 92.5%), a 5% LDPE layer, and a 2.5% EVOH layer. In one embodiment, the rollstock is white. In another embodiment, the rollstock is natural color. In one embodiment, the PP layer is white. In another embodiment, the PP layer is natural color. In another embodiment, the rollstock is made from XPP 803 material grade.

[0297] III.C. Example—XPP Reinforced Barrier Polypropylene for Thermoformed and Form-Fill-Seal Food Packaging III.C.1. Design In one aspect, XPP is a mono-material polypropylene roll stock that provides enhanced OTR and MVTR barrier without the use of special barrier materials or coatings for thermoform and form-fill-seal food packaging applications.

[0298] In one embodiment, the extruded rigid plastic roll stock of the present invention is used in thermoforming and FFS processes for various food packaging applications. However, XPP reinforced barrier polypropylene roll stock offers improvements to key performance criteria to achieve key performance requirements, including:

[0299] Alternatives to PS in Food Packaging to Comply with Proposition 65 Guidelines

[0300] Improved barrier performance

[0301] Improved sustainability and recyclability

[0302] Compatibility with existing equipment and processes

[0303] Drop-in replacement for polystyrene in form-fill-seal processes

[0304] In one aspect, packages made from the rollstock of the present invention successfully protect the biological, chemical, and / or physical integrity of products. Polyolefins inherently have excellent moisture vapor transmission rates (MVTR), but require the use of barrier materials such as EVOH to achieve the oxygen barrier protection required for shelf-stable, long-shelf-life food packaging. The polymeric film structures of the present invention offer dramatic improvements in both oxygen transmission rates (OTR) and MVTR compared to other general-purpose thermoplastic materials, and in some embodiments, provide the following without the use of specialized barrier materials or coatings: 90% / 90% improvement in OTR / MVTR over conventional polypropylene 100% / 150% improvement in OTR / MVTR vs. polystyrene

[0305] This improvement in barrier properties allows for the use of polymer film structures in packaging applications where traditional functional barrier materials, such as EVOH or nylon, were the only solution. As a result, material solutions are simplified and therefore more easily recyclable. In addition, polypropylene materials offer greater thermal stability than polystyrene and polyethylene terephthalate, allowing for use in freezer and microwave applications without compromising the integrity of the product or packaging.

[0306] Packing / Processing Efficiency: The polymer film structures of the present invention are produced from polypropylene, thus offering a 12% density reduction compared to PS and a 30% density reduction compared to PET. This density reduction results in higher yields (more parts) during the thermoforming process, lighter parts, less solid waste by weight, and reduced material usage compared to PS and PET.

[0307] The polymeric film structures of the present invention are advantageous for the life cycle of the package as demonstrated by the following.

[0308] III.C.2. Recyclability In one aspect, compared to other barrier material structures produced from complex blends of materials, the polymer film structures of the present invention are produced from polypropylene materials and therefore can be recycled using polypropylene resin ID code #5. Comparative barrier materials, such as HIPS / PVDC, must use resin ID code #7, which limits opportunities for recycling and reuse in other applications. In addition, the polymer film structures of the present invention can be processed similarly to other thermoplastic resins (without crosslinking) and therefore can be easily recycled. The polymer film structures of the present invention can be recycled multiple times in a closed-loop system or as part of a circular economy without losing their structural integrity. Thus, the polymer film structures of the present invention can be recycled back into various practical applications while maintaining their mechanical properties after multiple thermal cycles.

[0309] III.C.3. Material reduction In one aspect, the increased hardness and stiffness of the polymer film structure of the present invention not only enables drop-in processing for polystyrene replacement initiatives, but also provides the opportunity to downgauge the material structure, resulting in reduced material usage, increased yield, and lighter parts. For example, in one embodiment, the polymer film structure of the present invention allows thermoforming using 0.0175-inch roll stock with equivalent barrier results and similar functional and processing characteristics in the formed part as a result of the increased stiffness attributes of the polymer film structure of the present invention. By comparison, commercially available structures used for similar parts are typically produced using 0.020-inch high impact polystyrene (HIPS) roll stock. This example represents a 12.5% ​​reduction in gauge, which equates to a potential reduction in annual plastic material use, amounting to hundreds of thousands of pounds. This reduction would exceed the material savings that could potentially be realized through material substitution as a result of polypropylene's light weight and low density.

[0310] III.C.4. Performance Runs on existing packaging machines In one aspect, the polymeric film structures of the present invention provide enhanced stiffness and controlled shrinkage, thereby enabling processing on existing thermoforming and FFS platforms without the need for modifications or additional capital expenditures.

[0311] III.C.5. Controlled Contraction In one aspect, the polymeric film structures of the present invention provide controlled shrinkage, allowing for drop-in processing on existing thermoform and form-fill-seal systems and platforms. This is an inherent feature of the material and is achieved without the use of inorganic fillers such as talc or calcium carbonate, thus preserving polypropylene density and sortability for subsequent recycling.

[0312] III.C.6. Increased Stiffness Conventional polystyrene (PS) materials offer a flexural modulus / stiffness number of approximately 300 KPsi. By comparison, in one aspect of the present invention, XPP materials offer greater than 30% improved stiffness, resulting in a stronger, stiffer film compared to conventional PP and PS. This increase in stiffness and stiffness maintains the "snap-ability" and "scorability" of PS required in certain form-fill-seal multipack applications. This important functionality enables application versatility and the ability to replace traditionally non-recyclable materials, such as high impact polystyrene (HIPS) and polyvinylidene chloride (PVDC), with a fully recyclable solution without sacrificing functional attributes and processing properties.

[0313] The polymeric film structures of the present invention, which are thin gauge rollstocks, can serve as a drop-in material replacement solution for PS in rigid thermoform and form-fill-seal packaging. The polymeric film structures of the present invention can be successfully prepared on equipment designed for processing PS for food packaging applications without significant modifications to existing equipment and platforms.

[0314] III.C.7. Environmental Impact The global demand for reduced plastic waste and more sustainable packaging solutions, combined with health and safety concerns as a result of Proposition 65, has led to widespread initiatives to replace polystyrene (PS), the preferred material for form-fill-seal processes, in food packaging applications. In one embodiment, XPP rollstock enables food packaging to successfully transition away from PS, replacing it with the sustainable, recyclable, Proposition 65-compliant polymer film structure of the present invention.

[0315] Additionally, the low density and lightweight nature of polypropylene allows for more sustainable packaging, resulting in less solid waste by weight, less CO2 equivalent by weight, lower fuel consumption, and fewer emissions. The enhanced stiffness attributes of the polymer film structures of the present invention also allow for downgauging of existing structures, which significantly reduces overall material usage. Additionally, the inherent barrier properties of the polymer film structures of the present invention allow for simplified construction and easier recycling.

[0316] In one aspect, the polymeric film structures of the present invention provide inherent barrier improvements compared to other commercially available packaging materials without the use of inorganic fillers or additives. These improvements to barrier properties provide opportunities to optimize the structure and, in some cases, reduce or eliminate the use of additional materials typically found in barrier packaging structures, depending on the application.

[0317] The polymeric film structures of the present invention comprise polypropylene and are therefore recyclable in polypropylene recycle streams.

[0318] The inherent barrier properties of the polymeric film structures of the present invention, along with the versatility of the material's applications, may enable extended shelf life of commercially packaged food products, thus contributing to the long-term goal of reducing waste.

[0319] IV. Oxygen barrier properties The table below summarizes the nanoindentation data for Monolayer Sample A (regular PP) and Monolayer B (comprising a polypropylene two-layer stack). Tests were performed using two different tip geometries (one conical and one "Berkovich" or three-sided pyramid). Several shorter tests (5 seconds load, 2 seconds hold, and 5 seconds unload) and several longer tests (20 seconds load, 30 seconds hold, 20 seconds unload) were also performed, each to a maximum load of 1 mN.

[0320] In the first step, the sample was firmly bonded to a magnetic specimen disk. 40 indentations were then performed, and the average and standard deviation were calculated. The table below shows the modulus and hardness values ​​at different tip loads and test durations. Note that the conical tip indentations showed higher measured hardness. This can be expected since the conical tip causes less deformation at lower loads when compared to the sharper Berkovich tip.

[0321] From the observations, the polymer film structure of the present invention, designated elsewhere as XPP, exhibited a higher surface modulus and hardness in a statistically significant manner when compared to PP.

[0322] Without wishing to be bound by theory, the crystallization rates of conventional PP (A) and XPP (B) are significantly different, such that the crystallite size and density, and therefore the microstructure formed during extrusion of these materials, are clearly different. As a result, this leads to different hardness and modulus measurements at the "nanoscale," as evidenced by the data below. The data also further demonstrate the bulk tensile and flexural properties obtained for specimens made from PP (A and A') and XPP (B), which show material differences in modulus, stiffness, and flexural strength properties between the two materials, A and B. For example, when a sandwich structure, A / B / A', is coextruded with the above materials, the crystallization rate, and therefore the microstructure in the bulk region, exhibit similar performance, as shown below, with a gradient of properties across the interphase / interphase regions of the two, A / B and B / A'.

[0323] In terms of transport phenomena (in this case oxygen permeation through bulk materials A and B and sandwich structure A / B / A), the transport and barrier data were found to directionally follow the crystallization kinetics of these polymer film structures and the microstructure formed after extrusion.

[0324] Material A exhibits the lowest barrier, which translates into a lower % crystallinity, larger distinct crystalline domains, and a lower crystalline density.

[0325] Material B exhibits a high barrier that can be attributed to the nucleating agent, which facilitates rapid crystal formation, higher % crystallinity as evidenced by DSC, and less well-defined higher crystal density and random crystal formation.

[0326] When materials A and B are combined and coextruded into an A / B / A' structure, the same dynamics described above occur, but the "material" differences are evident in the discontinuities and / or gradients of properties (collectively "discontinuities") that occur at the A / B and B / A' interfaces. Without wishing to be bound by any theory, it is speculated that the discontinuity from one type of microstructure to another disrupts transport phenomena. Essentially, this discontinuity creates a more tortuous path for oxygen molecules to travel from the bulk A polymer to the A / B interface / interphase, into the bulk B polymer, and then into the B / A' interphase region and into the bulk A' polymer. This effectively explains why the A / B / A' structure has a 2-3 times higher barrier performance (oxygen barrier) compared to the bulk B specimen.

[0327] [Table 10]

Claims

1. A coextruded multilayer polymer film comprising at least one bilayer stack A-B1 or A-B2, wherein a first layer of the bilayer stack is A and a second layer of the bilayer stack is either B1 or B2; A is a layer mainly containing polypropylene, B1 is a layer containing mainly polypropylene and up to 50% by weight of a hydrocarbon resin; B2 is a layer containing primarily IMPEDE® polymer; A coextruded multilayer polymeric film, wherein the two layers in the two-layer stack are contiguous and adjacent to one another.

2. (A) at least one layer primarily comprising a polyolefin; (B) at least one layer comprising primarily polypropylene; (C) at least one layer comprising predominantly IMPEDE®; (D) at least one layer comprising primarily polypropylene and up to 50% by weight of a hydrocarbon resin; (E) at least one layer comprising predominantly a polyethylene polymer or interpolymer; (F) at least one barrier layer comprising EVOH; (G) at least one barrier layer comprising primarily nylon; (H) at least one barrier layer comprising primarily polyester; (I) at least one tie layer; and 10. The coextruded multilayer polymer film of claim 1, further comprising (J) one layer from a set of layers, or two or more layers from a set of layers, that is a combination of the above layers.

3. (I) an outer layer comprising polyethylene; (II) a core layer comprising EVOH; (III) an inner layer comprising polyethylene; 10. The coextruded multilayer polymeric film of claim 1, wherein at least one of said three layers comprises said two-layer stack.

4. The coextruded multilayer polymeric film of claim 3 , wherein the outer layer and the inner layer comprise the two-layer stack.

5. (I) a first layer comprising primarily polypropylene; (II) (a) Predominantly polypropylene and up to 50% by weight of a hydrocarbon resin; or (b) a second layer comprising primarily an IMPEDE® polymer; and (III) a third layer comprising primarily polypropylene.

6. 1. A coextruded multilayer polymer film comprising: (I) an outer layer stack comprising one or more layers, (A) optionally, at least one layer of the outer layer stack comprises a polyethylene polymer or a polyethylene interpolymer; (B) Optionally, the outer layer stack comprises: (i) a layer comprising primarily polypropylene, and (ii) (a) Predominantly polypropylene and up to 50% by weight of a hydrocarbon resin; or (b) a layer comprising primarily an IMPEDE® polymer; an outer layer stack, the two layers in the two-layer stack being contiguous with one another; (II) a core layer stack, comprising one or more layers; (C) optionally, at least one layer of the core layer stack comprises a polyethylene polymer or a polyethylene interpolymer; (D) Optionally, the core layer stack comprises: (iii) a layer comprising primarily polypropylene, and (iv) (a) Predominantly polypropylene and up to 50% by weight of a hydrocarbon resin; or (b) a layer comprising primarily an IMPEDE® polymer; the two layers in the two-layer stack are contiguous and adjacent to each other; (E) optionally, a core layer stack, wherein at least one layer of the core layer stack comprises EVOH; and (III) an inner layer stack comprising one or more layers, (F) optionally, at least one layer of the inner layer stack comprises a polyethylene polymer or a polyethylene interpolymer; (G) Optionally, the inner layer stack comprises: (v) a layer comprising primarily polypropylene, and (vi) (a) Predominantly polypropylene and up to 50% by weight of a hydrocarbon resin; or (b) a layer comprising primarily an IMPEDE® polymer; the two layers in the two-layer stack being contiguous with each other; and an inner layer stack; the polyethylene interpolymer (a) optionally, 0.894 to 0.908 g / cm ３ a first ethylene / α-olefin copolymer fraction having a density in the range of 0.2 to 1 dg / min; (b) optionally, from about 0.910 to 0.924 g / cm ３ a second ethylene / α-olefin copolymer fraction having a density in the range of 0.5 to 2 g / 10 min, a melt index in the range of 0.5 to 2 g / 10 min, a zero shear viscosity ratio (ZSVR) in the range of about 1.15 to 2.5, and a molecular weight distribution, expressed as the ratio of weight average molecular weight to number average molecular weight (Mw / Mn), in the range of 2.0 to 4.

0.

7. 3. The coextruded multilayer polymer film of claim 2, comprising a number of layers selected from the range of 2 to 100 layers.

8. 3. The coextruded multilayer polymer film of claim 2, wherein the weight percent of the EVOH copolymer relative to the coextruded multilayer polymer film ranges from about 0.1% to about 10%.

9. 9. The coextruded multilayer polymer film of claim 8, wherein the mole percent of ethylene in the EVOH copolymer ranges from about 10% to about 55%.

10. 10. The coextruded multilayer polymer film of claim 1, wherein the coextruded multilayer polymer film exhibits a DTUL of 30°C or greater and a secant modulus of 500 MPa or greater.

11. 10. The coextruded multilayer polymer film of claim 1, wherein the thickness of the film ranges from about 5 μm to about 1600 μm.

12. 2. The coextruded multilayer polymer film of claim 1, wherein the hydrocarbon resin in the second layer B1 comprises an aliphatic hydrocarbon resin, an aliphatic / aromatic hydrocarbon resin, an aromatic hydrocarbon resin, a polyterpene resin, a terpene phenolic resin, a rosin ester, a rosin acid, or a mixture thereof.

13. 10. The coextruded multilayer polymer film of claim 1, wherein the hydrocarbon resin in the second layer B1 is partially hydrogenated or fully hydrogenated.

14. 10. The coextruded multilayer polymer film of claim 1, wherein the hydrocarbon resin in the second layer B1 comprises polycyclopentadiene.

15. 10. The coextruded multilayer polymer film of claim 1, wherein the hydrocarbon resin in the second layer B1 has a weight average molecular weight of about 400 g / mol to about 5,000 g / mol.

16. 10. The coextruded multilayer polymer film of claim 1, wherein the hydrocarbon resin comprises an aromatic C9 hydrogenated resin having a Ring and Ball softening point of 110°C or greater.

17. 3.0 cm ３ / m ２ / day or less, and / or ３ / 100in ２ 10. The coextruded multilayer polymer film of claim 1, characterized by an oxygen transmission rate of 1000 ppm or less per 1000 ppm of water per day.

18. 10. The coextruded multilayer polymer film of claim 1, wherein the second layer B1 further comprises a nucleating agent selected from sodium benzoate, talc, glycerol alkoxide salts, cyclic carboxylates, bicyclic carboxylates, glycerolates, phosphines, phosphates, diols, hexahydrophthalates, amides, and sugar alcohols.

19. The nucleating agent is Mannitol or a mannitol-based compound, sorbitol or a sorbitol-based compound, nonitol or a nonitol-based compound, 1,2,3-trideoxy-4,6:5,7-bis-0-((4-propylphenyl)methylene)nonitol, 2,4,8,10-tetra(tert-butyl)-6-hydroxy-12H-dibenzo[d,g][1,3,2]dioxaphosphocine 6-oxide, a salt of 2,4,8,10-tetra(tert-butyl)-6-hydroxy-12H-dibenzo[d,g][1,3,2]dioxaphosphocine 6-oxide, a sodium salt of 2,4,8,10-tetra(tert-butyl)-6-hydroxy-12H-dibenzo[d,g][1,3,2]dioxaphosphocine 6-oxide, hydroxy-bis[2,2′-methylenebis[4,6-di(tert-butyl)phenyl]phosphate, 2,2′-methylenebis(4,6-di-tert-butylphenyl)phosphate, salts thereof, sodium salts thereof, aluminum salts thereof, and lithium salts thereof; (1R)-1-[(4R,4aR,8aS)-2,6-bis(3,4-dimethylphenyl)-4,4a,8,8a-tetrahydro-[1,-3]dioxino[5,4-d][1,3]dioxin-4-yl]ethane-1,2-diol, 1-[8-propyl-2,6-bis(4-propylphenyl)-4,4a,8,8a-tetrahydro-[1,3]dioxino[5,4-d][1,3]dioxin-4-yl]ethane-1,2-diol, N-[3,5-bis(2,2-dimethylpropanoylamino)phenyl]-2,2-dimethylpropanamide), (1S,2R)-cyclohexane-1,2-dicarboxylate salt and zinc octadecenoate, (1S,2R)-cyclohexane-1,2-dicarboxylate calcium salt and zinc octadecenoate, cis-endo-bicyclo[2,2,1]heptane-2,3-dicarboxylic acid disodium salt and 13-docosenamid, amorphous silicon dioxide, Bicycloheptanedicarboxylic acid, bicyclo[2.2.1]heptanedicarboxylate, Cyclohexanedicarboxylic acid, the calcium salt of cyclohexanedicarboxylic acid, a blend of cyclohexanedicarboxylic acid, the calcium salt of cyclohexanedicarboxylic acid, and zinc stearate, and The coextruded multilayer polymer film of claim 10, wherein the nucleating agent is selected from a mixture of two or more of these nucleating agents.

20. A molded polymeric article comprising the coextruded multilayer polymeric film of claim 1.

21. 21. The shaped polymeric article of claim 20, wherein the shaped polymeric article is a thermoformed shaped polymeric article.

22. 21. The shaped polymeric article of claim 20, which is a container for packaging food products.

23. The coextruded multilayer polymer film comprises: (A) at least one layer primarily comprising a polyolefin; (B) at least one layer comprising primarily polypropylene; (C) at least one layer comprising predominantly IMPEDE®; (D) at least one layer comprising primarily polypropylene and up to 50% by weight of a hydrocarbon resin; (E) at least one layer comprising predominantly a polyethylene polymer or interpolymer; (F) at least one barrier layer comprising EVOH; (G) at least one barrier layer comprising primarily nylon; (H) at least one barrier layer comprising primarily polyester; (I) at least one tie layer; and 23. The container of claim 22, further comprising (J) one layer from a set of layers, or two or more layers from a set of layers, that is a combination of the layers described above.

24. The coextruded multilayer polymer film comprises: (I) an outer layer comprising polyethylene; (II) a core layer comprising EVOH; (III) an inner layer comprising polyethylene; 24. The container of claim 23, wherein at least one of the three layers comprises the two-layer stack.

25. 25. The container of claim 24, wherein the outer layer and the inner layer comprise the two-layer stack.

26. The coextruded multilayer polymer film comprises: (I) a first layer comprising primarily polypropylene; (II) (a) Predominantly polypropylene and up to 50% by weight of a hydrocarbon resin; or (b) a second layer comprising primarily an IMPEDE® polymer; and 25. The container of claim 24, comprising three layers in this order: (III) a third layer comprising primarily polypropylene.

27. The coextruded multilayer polymer film comprises: (I) an outer layer stack comprising one or more layers, (A) optionally, at least one layer of the outer layer stack comprises a polyethylene polymer or a polyethylene interpolymer; (B) Optionally, the outer layer stack comprises: (i) a layer comprising primarily polypropylene, and (ii) (a) Predominantly polypropylene and up to 50% by weight of a hydrocarbon resin; or (b) a layer comprising primarily an IMPEDE® polymer; an outer layer stack, the two layers in the two-layer stack being contiguous with one another; (II) A core layer stack comprising one or more layers, (C) optionally, at least one layer of the core layer stack comprises a polyethylene polymer or a polyethylene interpolymer; (D) Optionally, the core layer stack comprises: (iii) a layer comprising primarily polypropylene, and (iv) (a) Predominantly polypropylene and up to 50% by weight of a hydrocarbon resin; or (b) a layer comprising primarily an IMPEDE® polymer; the two layers in the two-layer stack are contiguous and adjacent to each other; (E) optionally, a core layer stack, wherein at least one layer of the core layer stack comprises EVOH; and (III) an inner layer stack comprising one or more layers, (F) optionally, at least one layer of the inner layer stack comprises a polyethylene polymer or a polyethylene interpolymer; (G) Optionally, the inner layer stack comprises: (v) a layer comprising primarily polypropylene, and (vi) (a) Predominantly polypropylene and up to 50% by weight of a hydrocarbon resin; or (b) a layer comprising primarily an IMPEDE® polymer; the two layers in the two-layer stack being contiguous with each other; and an inner layer stack; the polyethylene interpolymer (a) optionally, 0.894 to 0.908 g / cm ３ a first ethylene / α-olefin copolymer fraction having a density in the range of 0.2 to 1 dg / min; (b) optionally, from about 0.910 to 0.924 g / cm ３ a second ethylene / α-olefin copolymer fraction having a density in the range of 0.5 to 2 g / 10 min, a melt index in the range of 0.5 to 2 g / 10 min, a zero shear viscosity ratio (ZSVR) in the range of about 1.15 to 2.5, and a molecular weight distribution, expressed as the ratio of weight average molecular weight to number average molecular weight (Mw / Mn), in the range of 2.0 to 4.

0.

28. 25. The container of claim 24, wherein the coextruded multilayer polymeric film comprises a number of layers selected from the range of 2 to 100 layers.

29. 24. The container of claim 23, wherein the weight percent of the EVOH copolymer relative to the coextruded multilayer polymer film ranges from about 0.1% to about 10%.

30. 30. The container of claim 29, wherein the mole percent of ethylene in the EVOH copolymer ranges from about 10% to about 55%.

31. 10. A process for preparing the coextruded multilayer polymer film of claim 1, comprising: (I) providing a layer A1; (II) providing a layer comprising B1 or B2, wherein the A1 and the B1, or the A1 and B2, form an interface or interphase at their adjacent boundary, such that the interphase provides a discontinuity in properties between the two layers, resulting in improved barrier properties of the coextruded multilayer polymer film.

32. 32. A container for packaging food products prepared from a rigid coextruded multilayer polymeric film prepared by the process of claim 31.

33. 20. A molded polymeric article comprising the coextruded multilayer polymeric film of claim 19.

34. 34. The shaped polymeric article of claim 33, wherein the shaped polymeric article is a thermoformed shaped polymeric article.

35. A laminate structure comprising a coextruded multilayer polymer film, said polymer film comprising at least one bilayer stack A-B1 or A-B2; the first layer of the two-layer stack is A and the second layer of the two-layer stack is either B1 or B2; A is a layer mainly containing polypropylene, B1 is a layer containing mainly polypropylene and up to 50% by weight of a hydrocarbon resin; B2 is a layer containing primarily IMPEDE® polymer; the two layers in the two-layer stack are contiguous and adjacent to each other; The thickness of the laminated structure is in the range of 5 μm to 1600 μm.

Images